molbuilder 1.0.0__py3-none-any.whl

molbuilder/reactions/knowledge_base.py

@@ -0,0 +1,1716 @@
+"""Curated reaction knowledge base with ~80 reaction templates.
+
+Every template is a ``ReactionTemplate`` instance that captures the
+reagents, conditions, selectivity cues, functional-group requirements,
+and retrosynthetic disconnections needed by the synthesis planner.
+
+Use the lookup helpers at the bottom of the module to query the
+database by functional group, category, or name.
+"""
+
+from molbuilder.reactions.reaction_types import ReactionTemplate, ReactionCategory
+
+# =====================================================================
+#  Master list of reaction templates
+# =====================================================================
+
+REACTION_TEMPLATES: list[ReactionTemplate] = []
+
+# Helper to build and register in one step
+def _t(**kw) -> ReactionTemplate:
+    tmpl = ReactionTemplate(**kw)
+    REACTION_TEMPLATES.append(tmpl)
+    return tmpl
+
+
+# -----------------------------------------------------------------
+#  SUBSTITUTION  (~10)
+# -----------------------------------------------------------------
+
+_t(
+    name="SN2 hydroxide on primary alkyl halide",
+    named_reaction="SN2",
+    category=ReactionCategory.SUBSTITUTION,
+    reagents=["NaOH"],
+    solvents=["DMSO", "DMF"],
+    temperature_range=(25.0, 80.0),
+    typical_yield=(70.0, 95.0),
+    functional_group_required=["alkyl_halide"],
+    functional_group_produced=["alcohol"],
+    functional_group_incompatible=["ester"],
+    mechanism="Back-side nucleophilic attack by hydroxide on the electrophilic carbon with simultaneous departure of the leaving group, proceeding through a single pentacoordinate transition state.",
+    reverse_transform="Disconnect C-OH bond; re-attach halide to carbon.",
+    safety_notes="NaOH is corrosive (H314).",
+)
+
+_t(
+    name="SN2 cyanide on primary alkyl halide",
+    named_reaction="SN2 cyanide displacement",
+    category=ReactionCategory.SUBSTITUTION,
+    reagents=["NaCN"],
+    solvents=["DMSO", "DMF"],
+    temperature_range=(25.0, 80.0),
+    typical_yield=(65.0, 90.0),
+    functional_group_required=["alkyl_halide"],
+    functional_group_produced=["nitrile"],
+    functional_group_incompatible=[],
+    mechanism="Cyanide ion attacks electrophilic carbon in an SN2 fashion, extending the carbon chain by one.",
+    reverse_transform="Disconnect C-CN bond; replace CN with halide.",
+    safety_notes="NaCN is acutely toxic (H300/H310/H330). Handle in fume hood with cyanide antidote kit available.",
+)
+
+_t(
+    name="SN2 azide on primary alkyl halide",
+    named_reaction="SN2 azide displacement",
+    category=ReactionCategory.SUBSTITUTION,
+    reagents=["NaN3"],
+    solvents=["DMF", "DMSO"],
+    temperature_range=(25.0, 60.0),
+    typical_yield=(75.0, 95.0),
+    functional_group_required=["alkyl_halide"],
+    functional_group_produced=["azide"],
+    functional_group_incompatible=[],
+    mechanism="Azide ion displaces halide in a concerted SN2 mechanism.",
+    reverse_transform="Disconnect C-N3 bond; replace azide with halide.",
+    safety_notes="NaN3 is highly toxic and forms explosive heavy-metal azides with Cu/Pb. Never acidify waste.",
+)
+
+_t(
+    name="SN1 tertiary halide solvolysis",
+    named_reaction="SN1",
+    category=ReactionCategory.SUBSTITUTION,
+    reagents=[],
+    solvents=["water", "EtOH", "AcOH"],
+    temperature_range=(25.0, 80.0),
+    typical_yield=(50.0, 85.0),
+    functional_group_required=["alkyl_halide"],
+    functional_group_produced=["alcohol"],
+    functional_group_incompatible=[],
+    mechanism="Ionisation of the tertiary halide generates a carbocation, which is captured by the solvent nucleophile.",
+    reverse_transform="Disconnect C-OH; reattach halide on the tertiary carbon.",
+)
+
+_t(
+    name="Gabriel synthesis",
+    named_reaction="Gabriel synthesis",
+    category=ReactionCategory.SUBSTITUTION,
+    reagents=["potassium phthalimide", "N2H4"],
+    solvents=["DMF", "EtOH"],
+    temperature_range=(25.0, 100.0),
+    typical_yield=(60.0, 85.0),
+    functional_group_required=["alkyl_halide"],
+    functional_group_produced=["primary_amine"],
+    functional_group_incompatible=[],
+    mechanism="Phthalimide anion displaces halide (SN2); subsequent hydrazinolysis liberates the primary amine.",
+    reverse_transform="Disconnect C-NH2; replace amine with halide.",
+)
+
+_t(
+    name="Finkelstein reaction",
+    named_reaction="Finkelstein reaction",
+    category=ReactionCategory.SUBSTITUTION,
+    reagents=["NaI"],
+    solvents=["acetone"],
+    temperature_range=(25.0, 60.0),
+    typical_yield=(75.0, 95.0),
+    functional_group_required=["alkyl_halide_cl", "alkyl_halide_br"],
+    functional_group_produced=["alkyl_halide_i"],
+    functional_group_incompatible=[],
+    mechanism="Iodide displaces chloride or bromide in acetone; NaCl or NaBr precipitates, driving equilibrium.",
+    reverse_transform="Replace iodide with the original halide.",
+)
+
+_t(
+    name="Mitsunobu reaction",
+    named_reaction="Mitsunobu reaction",
+    category=ReactionCategory.SUBSTITUTION,
+    reagents=["PPh3", "DIAD", "nucleophile (phthalimide, carboxylic acid, etc.)"],
+    solvents=["THF"],
+    temperature_range=(0.0, 25.0),
+    typical_yield=(60.0, 90.0),
+    functional_group_required=["alcohol"],
+    functional_group_produced=["ester", "ether", "azide"],
+    functional_group_incompatible=[],
+    mechanism="PPh3/DIAD activate the alcohol with inversion; a pronucleophile (pKa < 11) displaces via SN2.",
+    reverse_transform="Disconnect the new C-nucleophile bond; restore the alcohol with inverted stereochemistry.",
+    safety_notes="DIAD/DEAD are toxic and flammable. Triphenylphosphine oxide byproduct complicates purification.",
+)
+
+_t(
+    name="Williamson ether synthesis",
+    named_reaction="Williamson ether synthesis",
+    category=ReactionCategory.SUBSTITUTION,
+    reagents=["NaH", "alkyl halide (primary)"],
+    solvents=["THF", "DMF"],
+    temperature_range=(0.0, 70.0),
+    typical_yield=(70.0, 95.0),
+    functional_group_required=["alcohol"],
+    functional_group_produced=["ether"],
+    functional_group_incompatible=["carboxylic_acid", "primary_amine"],
+    mechanism="NaH deprotonates the alcohol to form an alkoxide, which then displaces a primary halide via SN2.",
+    reverse_transform="Disconnect C-O-C; one fragment becomes alcohol, other becomes alkyl halide.",
+    safety_notes="NaH is pyrophoric when dry. Generates H2 gas.",
+)
+
+_t(
+    name="SN2 with KOtBu on primary halide",
+    named_reaction="SN2 (bulky base can give elimination side products)",
+    category=ReactionCategory.SUBSTITUTION,
+    reagents=["KOtBu"],
+    solvents=["DMSO", "THF"],
+    temperature_range=(25.0, 60.0),
+    typical_yield=(40.0, 75.0),
+    functional_group_required=["alkyl_halide"],
+    functional_group_produced=["ether"],
+    functional_group_incompatible=[],
+    mechanism="tert-Butoxide can act as nucleophile on unhindered substrates, but elimination (E2) competes.",
+    reverse_transform="Disconnect C-O-tBu; replace with halide.",
+    safety_notes="KOtBu is pyrophoric and moisture-sensitive.",
+)
+
+# -----------------------------------------------------------------
+#  ELIMINATION  (~6)
+# -----------------------------------------------------------------
+
+_t(
+    name="E2 elimination with KOtBu",
+    named_reaction="E2",
+    category=ReactionCategory.ELIMINATION,
+    reagents=["KOtBu"],
+    solvents=["THF", "t-BuOH"],
+    temperature_range=(25.0, 80.0),
+    typical_yield=(65.0, 90.0),
+    functional_group_required=["alkyl_halide"],
+    functional_group_produced=["alkene"],
+    functional_group_incompatible=[],
+    mechanism="Strong bulky base abstracts a beta-proton anti-periplanar to the leaving group in a concerted E2 mechanism.",
+    reverse_transform="Add H-X across the double bond.",
+    safety_notes="KOtBu is pyrophoric.",
+)
+
+_t(
+    name="E1 acid-catalyzed dehydration of alcohol",
+    named_reaction="E1 dehydration",
+    category=ReactionCategory.ELIMINATION,
+    reagents=["H2SO4"],
+    solvents=["neat", "toluene"],
+    temperature_range=(80.0, 180.0),
+    typical_yield=(50.0, 85.0),
+    functional_group_required=["alcohol"],
+    functional_group_produced=["alkene"],
+    functional_group_incompatible=["epoxide"],
+    mechanism="Protonation of the hydroxyl followed by loss of water generates a carbocation; loss of a beta-proton gives the alkene.",
+    reverse_transform="Add water across the double bond (acid-catalysed hydration).",
+    safety_notes="Concentrated H2SO4 is extremely corrosive.",
+)
+
+_t(
+    name="Hofmann elimination",
+    named_reaction="Hofmann elimination",
+    category=ReactionCategory.ELIMINATION,
+    reagents=["MeI (excess)", "Ag2O", "heat"],
+    solvents=["water"],
+    temperature_range=(100.0, 200.0),
+    typical_yield=(40.0, 70.0),
+    functional_group_required=["primary_amine", "secondary_amine", "tertiary_amine"],
+    functional_group_produced=["alkene"],
+    functional_group_incompatible=[],
+    mechanism="Exhaustive methylation of the amine followed by hydroxide-induced E2 elimination gives the less substituted (Hofmann) alkene.",
+    reverse_transform="Amino-alkylation of the less-substituted end of the alkene.",
+)
+
+_t(
+    name="Cope elimination",
+    named_reaction="Cope elimination",
+    category=ReactionCategory.ELIMINATION,
+    reagents=["mCPBA (to form N-oxide)", "heat"],
+    solvents=["DCM", "toluene"],
+    temperature_range=(80.0, 150.0),
+    typical_yield=(50.0, 80.0),
+    functional_group_required=["tertiary_amine"],
+    functional_group_produced=["alkene"],
+    functional_group_incompatible=[],
+    mechanism="Oxidation of a tertiary amine to the N-oxide, which undergoes syn-periplanar intramolecular elimination via a five-membered cyclic transition state.",
+    reverse_transform="Add amine across the double bond.",
+)
+
+_t(
+    name="Dehydrohalogenation with NaOEt",
+    named_reaction="E2 dehydrohalogenation",
+    category=ReactionCategory.ELIMINATION,
+    reagents=["NaOEt"],
+    solvents=["EtOH"],
+    temperature_range=(50.0, 80.0),
+    typical_yield=(60.0, 85.0),
+    functional_group_required=["alkyl_halide"],
+    functional_group_produced=["alkene"],
+    functional_group_incompatible=["ester"],
+    mechanism="Ethoxide base removes a beta-proton anti to the halide in a concerted E2 mechanism, favouring the Zaitsev product.",
+    reverse_transform="Add HX across the alkene.",
+)
+
+_t(
+    name="Zaitsev vs Hofmann selectivity (E2, size of base)",
+    named_reaction="E2 selectivity",
+    category=ReactionCategory.ELIMINATION,
+    reagents=["KOtBu (Hofmann)", "NaOEt (Zaitsev)"],
+    solvents=["THF", "EtOH"],
+    temperature_range=(25.0, 80.0),
+    typical_yield=(60.0, 85.0),
+    functional_group_required=["alkyl_halide"],
+    functional_group_produced=["alkene"],
+    functional_group_incompatible=[],
+    mechanism="Bulky bases (KOtBu) give the less-substituted (Hofmann) alkene; smaller bases (NaOEt) give the more-substituted (Zaitsev) alkene.",
+    reverse_transform="Add HX to the appropriate regiochemistry.",
+)
+
+# -----------------------------------------------------------------
+#  ADDITION  (~10)
+# -----------------------------------------------------------------
+
+_t(
+    name="HBr addition to alkene (Markovnikov)",
+    named_reaction="Electrophilic addition",
+    category=ReactionCategory.ADDITION,
+    reagents=["HBr"],
+    solvents=["DCM"],
+    temperature_range=(-10.0, 25.0),
+    typical_yield=(70.0, 90.0),
+    functional_group_required=["alkene"],
+    functional_group_produced=["alkyl_halide_br"],
+    functional_group_incompatible=["alcohol"],
+    mechanism="Protonation of the alkene forms the more stable carbocation (Markovnikov); bromide captures the cation.",
+    reverse_transform="Remove HBr from the alkyl bromide via E2.",
+)
+
+_t(
+    name="Anti-Markovnikov HBr addition (peroxide)",
+    named_reaction="Radical addition (anti-Markovnikov)",
+    category=ReactionCategory.ADDITION,
+    reagents=["HBr", "ROOR (peroxide initiator)"],
+    solvents=["CCl4", "pentane"],
+    temperature_range=(25.0, 80.0),
+    typical_yield=(60.0, 85.0),
+    functional_group_required=["alkene"],
+    functional_group_produced=["alkyl_halide_br"],
+    functional_group_incompatible=[],
+    mechanism="Peroxide generates Br radical; Br adds to the less substituted carbon giving the more stable radical, then H-atom transfer completes addition.",
+    reverse_transform="Remove HBr from anti-Markovnikov position.",
+    safety_notes="Peroxides are shock-sensitive. Use freshly prepared.",
+)
+
+_t(
+    name="Hydroboration-oxidation",
+    named_reaction="Hydroboration-oxidation",
+    category=ReactionCategory.ADDITION,
+    reagents=["BH3*THF (or 9-BBN)", "H2O2", "NaOH"],
+    solvents=["THF"],
+    temperature_range=(0.0, 25.0),
+    typical_yield=(70.0, 90.0),
+    functional_group_required=["alkene"],
+    functional_group_produced=["alcohol"],
+    functional_group_incompatible=["aldehyde", "ketone"],
+    mechanism="Syn addition of B-H across the double bond with anti-Markovnikov regioselectivity; oxidative workup replaces B with OH with retention.",
+    reverse_transform="Disconnect C-OH at the anti-Markovnikov position; restore alkene.",
+    safety_notes="BH3 is pyrophoric; handle under inert atmosphere.",
+)
+
+_t(
+    name="Epoxidation with mCPBA",
+    named_reaction="Prilezhaev epoxidation",
+    category=ReactionCategory.ADDITION,
+    reagents=["mCPBA"],
+    solvents=["DCM"],
+    temperature_range=(0.0, 25.0),
+    typical_yield=(70.0, 95.0),
+    functional_group_required=["alkene"],
+    functional_group_produced=["epoxide"],
+    functional_group_incompatible=["primary_amine", "thiol"],
+    mechanism="Concerted delivery of oxygen from the peracid to the alkene via a butterfly transition state; syn addition.",
+    reverse_transform="Open the epoxide to reveal the original alkene.",
+)
+
+_t(
+    name="Dihydroxylation with OsO4",
+    named_reaction="Upjohn dihydroxylation",
+    category=ReactionCategory.ADDITION,
+    reagents=["OsO4 (cat.)", "NMO"],
+    solvents=["acetone/water", "THF/water"],
+    catalysts=["OsO4"],
+    temperature_range=(0.0, 25.0),
+    typical_yield=(75.0, 95.0),
+    functional_group_required=["alkene"],
+    functional_group_produced=["diol"],
+    functional_group_incompatible=[],
+    mechanism="OsO4 adds across the alkene in a [3+2] cycloaddition to form an osmate ester; NMO re-oxidises Os(VI) to Os(VIII) catalytically. Syn diol is produced.",
+    reverse_transform="Convert 1,2-diol back to alkene (via periodate cleavage or Corey-Winter).",
+    safety_notes="OsO4 is extremely toxic and volatile. Use catalytic amounts with NMO co-oxidant.",
+)
+
+_t(
+    name="Catalytic hydrogenation of alkene",
+    named_reaction="Catalytic hydrogenation",
+    category=ReactionCategory.ADDITION,
+    reagents=["H2"],
+    solvents=["EtOAc", "MeOH", "EtOH"],
+    catalysts=["Pd/C", "PtO2"],
+    temperature_range=(20.0, 50.0),
+    typical_yield=(85.0, 99.0),
+    functional_group_required=["alkene"],
+    functional_group_produced=[],
+    functional_group_incompatible=["alkyl_halide_br", "azide"],
+    mechanism="Syn addition of H2 across the double bond on the catalyst surface.",
+    reverse_transform="Re-introduce unsaturation by dehydrogenation or elimination.",
+    safety_notes="H2 is extremely flammable. Pd/C can be pyrophoric when dry.",
+)
+
+_t(
+    name="Halogenation of alkene (Br2/CCl4)",
+    named_reaction="Halogenation",
+    category=ReactionCategory.ADDITION,
+    reagents=["Br2"],
+    solvents=["CCl4", "DCM"],
+    temperature_range=(-10.0, 25.0),
+    typical_yield=(75.0, 95.0),
+    functional_group_required=["alkene"],
+    functional_group_produced=["alkyl_halide_br"],
+    functional_group_incompatible=[],
+    mechanism="Bromine adds anti across the double bond via a bromonium ion intermediate. Both carbons receive Br (vicinal dibromide).",
+    reverse_transform="Remove two Br atoms by Zn in AcOH to restore the alkene.",
+    safety_notes="Br2 is highly corrosive and toxic. Work in fume hood.",
+)
+
+_t(
+    name="Acid-catalysed hydration of alkene",
+    named_reaction="Acid-catalysed hydration",
+    category=ReactionCategory.ADDITION,
+    reagents=["H2SO4 (cat.)", "H2O"],
+    solvents=["water/THF"],
+    temperature_range=(25.0, 80.0),
+    typical_yield=(50.0, 80.0),
+    functional_group_required=["alkene"],
+    functional_group_produced=["alcohol"],
+    functional_group_incompatible=["epoxide"],
+    mechanism="Protonation of the alkene gives the Markovnikov carbocation; water captures it to yield the alcohol after deprotonation.",
+    reverse_transform="Dehydrate the alcohol to the alkene.",
+)
+
+_t(
+    name="Ozonolysis",
+    named_reaction="Ozonolysis",
+    category=ReactionCategory.ADDITION,
+    reagents=["O3", "Me2S (or PPh3)"],
+    solvents=["DCM", "MeOH"],
+    temperature_range=(-78.0, -40.0),
+    typical_yield=(65.0, 90.0),
+    functional_group_required=["alkene"],
+    functional_group_produced=["aldehyde", "ketone"],
+    functional_group_incompatible=["thiol"],
+    mechanism="Ozone adds across the double bond via a [3+2]/retro-[3+2]/[3+2] sequence forming an ozonide; reductive workup (Me2S or PPh3) cleaves it to carbonyls.",
+    reverse_transform="Join two carbonyl fragments with a Wittig or McMurry coupling to reform the alkene.",
+    safety_notes="Ozone is a powerful oxidizer and respiratory hazard. Ozonides are explosive; always quench completely before workup.",
+)
+
+_t(
+    name="Simmons-Smith cyclopropanation",
+    named_reaction="Simmons-Smith",
+    category=ReactionCategory.ADDITION,
+    reagents=["CH2I2", "Zn-Cu couple (or ZnEt2)"],
+    solvents=["Et2O", "DCM"],
+    temperature_range=(0.0, 40.0),
+    typical_yield=(55.0, 85.0),
+    functional_group_required=["alkene"],
+    functional_group_produced=["cyclopropane"],
+    functional_group_incompatible=[],
+    mechanism="Zinc carbenoid (IZnCH2I) delivers CH2 to the less hindered face of the alkene in a concerted [2+1] cycloaddition.",
+    reverse_transform="Open the cyclopropane to reveal alkene + CH2 unit.",
+    safety_notes="CH2I2 is a lachrymator; ZnEt2 is pyrophoric.",
+)
+
+# -----------------------------------------------------------------
+#  OXIDATION  (~8)
+# -----------------------------------------------------------------
+
+_t(
+    name="PCC oxidation of primary alcohol to aldehyde",
+    named_reaction="PCC oxidation",
+    category=ReactionCategory.OXIDATION,
+    reagents=["PCC"],
+    solvents=["DCM"],
+    temperature_range=(20.0, 25.0),
+    typical_yield=(70.0, 90.0),
+    functional_group_required=["alcohol"],
+    functional_group_produced=["aldehyde"],
+    functional_group_incompatible=["primary_amine"],
+    mechanism="PCC oxidises the primary alcohol to the aldehyde stage and stops (no over-oxidation to carboxylic acid) because the mild conditions and anhydrous solvent prevent further oxidation.",
+    reverse_transform="Reduce aldehyde to primary alcohol (NaBH4).",
+    safety_notes="PCC contains Cr(VI) -- carcinogenic. Use minimum amount and dispose of Cr waste properly.",
+)
+
+_t(
+    name="Jones oxidation of alcohol to carboxylic acid / ketone",
+    named_reaction="Jones oxidation",
+    category=ReactionCategory.OXIDATION,
+    reagents=["CrO3", "H2SO4"],
+    solvents=["acetone"],
+    temperature_range=(0.0, 25.0),
+    typical_yield=(70.0, 90.0),
+    functional_group_required=["alcohol"],
+    functional_group_produced=["carboxylic_acid", "ketone"],
+    functional_group_incompatible=["alkene"],
+    mechanism="Cr(VI) oxidises primary alcohols all the way to carboxylic acids and secondary alcohols to ketones.",
+    reverse_transform="Reduce carboxylic acid/ketone back to alcohol.",
+    safety_notes="Cr(VI) is carcinogenic. Generate minimum chromium waste.",
+)
+
+_t(
+    name="Swern oxidation",
+    named_reaction="Swern oxidation",
+    category=ReactionCategory.OXIDATION,
+    reagents=["oxalyl chloride", "DMSO", "Et3N"],
+    solvents=["DCM"],
+    temperature_range=(-78.0, -40.0),
+    typical_yield=(75.0, 95.0),
+    functional_group_required=["alcohol"],
+    functional_group_produced=["aldehyde", "ketone"],
+    functional_group_incompatible=[],
+    mechanism="DMSO is activated by oxalyl chloride; the activated species oxidises the alcohol via an alkoxysulfonium intermediate. Triethylamine triggers intramolecular elimination to yield the carbonyl.",
+    reverse_transform="Reduce aldehyde/ketone back to alcohol.",
+    safety_notes="Must keep at -78 C to avoid Pummerer side reactions. DMSO/oxalyl chloride generates CO, CO2, and (CH3)2S (foul odour).",
+)
+
+_t(
+    name="KMnO4 oxidation of alkene",
+    named_reaction="Permanganate oxidation",
+    category=ReactionCategory.OXIDATION,
+    reagents=["KMnO4"],
+    solvents=["water/acetone", "water"],
+    temperature_range=(0.0, 100.0),
+    typical_yield=(50.0, 80.0),
+    functional_group_required=["alkene"],
+    functional_group_produced=["diol", "carboxylic_acid", "ketone"],
+    functional_group_incompatible=["aldehyde"],
+    mechanism="Cold dilute KMnO4 gives syn-dihydroxylation; hot concentrated KMnO4 cleaves the double bond to carboxylic acids/ketones.",
+    reverse_transform="Recombine fragments or reduce products.",
+    safety_notes="Strong oxidizer (H272). Purple waste can be quenched with sodium bisulfite.",
+)
+
+_t(
+    name="Dess-Martin periodinane oxidation",
+    named_reaction="Dess-Martin oxidation",
+    category=ReactionCategory.OXIDATION,
+    reagents=["Dess-Martin periodinane"],
+    solvents=["DCM"],
+    temperature_range=(20.0, 25.0),
+    typical_yield=(80.0, 98.0),
+    functional_group_required=["alcohol"],
+    functional_group_produced=["aldehyde", "ketone"],
+    functional_group_incompatible=[],
+    mechanism="Hypervalent iodine(V) reagent oxidises alcohols to carbonyls under very mild, neutral conditions with high functional-group tolerance.",
+    reverse_transform="Reduce carbonyl back to alcohol.",
+    safety_notes="Shock-sensitive when dry. Keep as solution.",
+)
+
+_t(
+    name="Baeyer-Villiger oxidation",
+    named_reaction="Baeyer-Villiger oxidation",
+    category=ReactionCategory.OXIDATION,
+    reagents=["mCPBA"],
+    solvents=["DCM"],
+    temperature_range=(0.0, 40.0),
+    typical_yield=(60.0, 90.0),
+    functional_group_required=["ketone"],
+    functional_group_produced=["ester"],
+    functional_group_incompatible=["primary_amine"],
+    mechanism="Peracid attacks the ketone to form a Criegee intermediate; 1,2-alkyl shift inserts an oxygen between the carbonyl carbon and the migrating group.",
+    reverse_transform="Disconnect the ester C-O bond; recombine as ketone.",
+)
+
+_t(
+    name="Sharpless asymmetric epoxidation",
+    named_reaction="Sharpless epoxidation",
+    category=ReactionCategory.OXIDATION,
+    reagents=["Ti(OiPr)4", "tBuOOH", "L-(+)-DIPT or D-(-)-DIPT"],
+    solvents=["DCM"],
+    catalysts=["Ti(OiPr)4"],
+    temperature_range=(-20.0, 0.0),
+    typical_yield=(70.0, 90.0),
+    functional_group_required=["alkene", "alcohol"],
+    functional_group_produced=["epoxide"],
+    functional_group_incompatible=["thiol"],
+    mechanism="Titanium-tartrate complex directs epoxidation of allylic alcohols with high enantioselectivity using tBuOOH as terminal oxidant.",
+    reverse_transform="Open epoxide to regenerate allylic alcohol.",
+    safety_notes="tBuOOH is an organic peroxide -- shock sensitive above certain concentrations.",
+)
+
+_t(
+    name="Wacker oxidation",
+    named_reaction="Wacker oxidation",
+    category=ReactionCategory.OXIDATION,
+    reagents=["PdCl2 (cat.)", "CuCl2 (co-cat.)", "O2"],
+    solvents=["DMF/water"],
+    catalysts=["PdCl2", "CuCl2"],
+    temperature_range=(25.0, 80.0),
+    typical_yield=(60.0, 85.0),
+    functional_group_required=["alkene"],
+    functional_group_produced=["ketone"],
+    functional_group_incompatible=[],
+    mechanism="Pd(II)-catalysed nucleophilic attack of water on the coordinated alkene (Markovnikov selectivity) gives a methyl ketone. CuCl2/O2 re-oxidises Pd(0) to Pd(II).",
+    reverse_transform="Disconnect CH3-C(=O)-R; rebuild terminal alkene.",
+)
+
+# -----------------------------------------------------------------
+#  REDUCTION  (~8)
+# -----------------------------------------------------------------
+
+_t(
+    name="NaBH4 reduction of aldehyde/ketone to alcohol",
+    named_reaction="NaBH4 reduction",
+    category=ReactionCategory.REDUCTION,
+    reagents=["NaBH4"],
+    solvents=["MeOH", "EtOH"],
+    temperature_range=(0.0, 25.0),
+    typical_yield=(80.0, 98.0),
+    functional_group_required=["aldehyde", "ketone"],
+    functional_group_produced=["alcohol"],
+    functional_group_incompatible=[],
+    mechanism="Hydride delivery from borohydride to the electrophilic carbonyl carbon gives an alkoxide, protonated on workup.",
+    reverse_transform="Oxidise alcohol to aldehyde/ketone.",
+)
+
+_t(
+    name="LiAlH4 reduction of ester to primary alcohol",
+    named_reaction="LiAlH4 reduction",
+    category=ReactionCategory.REDUCTION,
+    reagents=["LiAlH4"],
+    solvents=["THF", "Et2O"],
+    temperature_range=(0.0, 70.0),
+    typical_yield=(75.0, 95.0),
+    functional_group_required=["ester"],
+    functional_group_produced=["alcohol"],
+    functional_group_incompatible=["alkyl_halide", "nitrile"],
+    mechanism="Two equivalents of hydride reduce the ester first to an aldehyde (hemiacetal collapses) then to the primary alcohol.",
+    reverse_transform="Oxidise alcohol and re-esterify.",
+    safety_notes="LiAlH4 reacts violently with water and protic solvents. Quench with careful Fieser workup (H2O, NaOH, H2O).",
+)
+
+_t(
+    name="LiAlH4 reduction of amide to amine",
+    named_reaction="LiAlH4 reduction",
+    category=ReactionCategory.REDUCTION,
+    reagents=["LiAlH4"],
+    solvents=["THF"],
+    temperature_range=(0.0, 70.0),
+    typical_yield=(65.0, 90.0),
+    functional_group_required=["amide"],
+    functional_group_produced=["primary_amine", "secondary_amine", "tertiary_amine"],
+    functional_group_incompatible=["alkyl_halide"],
+    mechanism="LiAlH4 reduces the amide C=O completely, yielding the corresponding amine.",
+    reverse_transform="Oxidise amine back to amide (difficult) or form amide from amine + acyl chloride.",
+    safety_notes="LiAlH4 is pyrophoric. Use strict anhydrous conditions.",
+)
+
+_t(
+    name="DIBAL-H reduction of ester to aldehyde at -78 C",
+    named_reaction="DIBAL-H partial reduction",
+    category=ReactionCategory.REDUCTION,
+    reagents=["DIBAL-H"],
+    solvents=["DCM", "toluene"],
+    temperature_range=(-78.0, -60.0),
+    typical_yield=(60.0, 85.0),
+    functional_group_required=["ester"],
+    functional_group_produced=["aldehyde"],
+    functional_group_incompatible=[],
+    mechanism="At -78 C, DIBAL-H delivers one equivalent of hydride to the ester, stopping at the aluminium hemiacetal stage. Aqueous workup liberates the aldehyde.",
+    reverse_transform="Re-esterify the aldehyde fragment.",
+    safety_notes="DIBAL-H is pyrophoric. Strict -78 C temperature control is essential to prevent over-reduction.",
+)
+
+_t(
+    name="Catalytic hydrogenation (general)",
+    named_reaction="Catalytic hydrogenation",
+    category=ReactionCategory.REDUCTION,
+    reagents=["H2"],
+    solvents=["EtOAc", "MeOH", "EtOH"],
+    catalysts=["Pd/C", "PtO2", "Rh/C"],
+    temperature_range=(20.0, 50.0),
+    typical_yield=(85.0, 99.0),
+    functional_group_required=["alkene", "alkyne", "nitrile", "nitro"],
+    functional_group_produced=["alcohol", "primary_amine"],
+    functional_group_incompatible=[],
+    mechanism="Substrate adsorbs on metal surface; H2 dissociates and adds syn to the unsaturated bond.",
+    reverse_transform="Re-oxidise or dehydrogenate.",
+    safety_notes="H2 is highly flammable (H220). Pd/C can be pyrophoric when dry.",
+)
+
+_t(
+    name="Birch reduction",
+    named_reaction="Birch reduction",
+    category=ReactionCategory.REDUCTION,
+    reagents=["Na (or Li)", "NH3 (liquid)", "t-BuOH"],
+    solvents=["liquid NH3"],
+    temperature_range=(-78.0, -33.0),
+    typical_yield=(60.0, 85.0),
+    functional_group_required=["aromatic_ring"],
+    functional_group_produced=["alkene"],
+    functional_group_incompatible=["alkyl_halide_br"],
+    mechanism="Dissolving metal (Na/Li in liq. NH3) delivers electrons to the aromatic ring; proton source (t-BuOH) quenches the radical anion to give 1,4-cyclohexadienes.",
+    reverse_transform="Re-aromatise by oxidation (DDQ or Pd/C).",
+    safety_notes="Liquid NH3 is extremely hazardous (bp -33 C). Na metal is pyrophoric. Requires cold-finger condenser.",
+)
+
+_t(
+    name="Wolff-Kishner reduction",
+    named_reaction="Wolff-Kishner reduction",
+    category=ReactionCategory.REDUCTION,
+    reagents=["N2H4", "KOH"],
+    solvents=["diethylene glycol", "ethylene glycol"],
+    temperature_range=(180.0, 230.0),
+    typical_yield=(60.0, 85.0),
+    functional_group_required=["aldehyde", "ketone"],
+    functional_group_produced=[],
+    functional_group_incompatible=["ester", "alkyl_halide"],
+    mechanism="Hydrazone formation followed by base-mediated decomposition with loss of N2 converts C=O to CH2.",
+    reverse_transform="Oxidise the methylene back to carbonyl.",
+    safety_notes="Hydrazine is toxic and carcinogenic (H350). Very high temperatures required.",
+)
+
+_t(
+    name="Clemmensen reduction",
+    named_reaction="Clemmensen reduction",
+    category=ReactionCategory.REDUCTION,
+    reagents=["Zn(Hg)", "HCl (conc.)"],
+    solvents=["water/HCl"],
+    temperature_range=(80.0, 110.0),
+    typical_yield=(55.0, 80.0),
+    functional_group_required=["aldehyde", "ketone"],
+    functional_group_produced=[],
+    functional_group_incompatible=["alcohol", "primary_amine"],
+    mechanism="Zinc amalgam in concentrated HCl reduces the carbonyl to a methylene group under acidic conditions (complement to Wolff-Kishner which uses base).",
+    reverse_transform="Oxidise the methylene back to carbonyl.",
+    safety_notes="Uses mercury amalgam (environmental hazard) and concentrated HCl.",
+)
+
+_t(
+    name="Luche reduction (NaBH4/CeCl3)",
+    named_reaction="Luche reduction",
+    category=ReactionCategory.REDUCTION,
+    reagents=["NaBH4", "CeCl3*7H2O"],
+    solvents=["MeOH"],
+    temperature_range=(-10.0, 0.0),
+    typical_yield=(75.0, 95.0),
+    functional_group_required=["ketone"],
+    functional_group_produced=["alcohol"],
+    functional_group_incompatible=[],
+    mechanism="CeCl3 activates the carbonyl as a hard electrophile, directing NaBH4 to achieve selective 1,2-reduction of enones (leaving conjugated alkene intact).",
+    reverse_transform="Oxidise allylic alcohol back to enone.",
+)
+
+# -----------------------------------------------------------------
+#  COUPLING  (~10)
+# -----------------------------------------------------------------
+
+_t(
+    name="Grignard addition to aldehyde",
+    named_reaction="Grignard reaction",
+    category=ReactionCategory.COUPLING,
+    reagents=["RMgBr"],
+    solvents=["THF", "Et2O"],
+    temperature_range=(-20.0, 25.0),
+    typical_yield=(70.0, 95.0),
+    functional_group_required=["aldehyde"],
+    functional_group_produced=["alcohol"],
+    functional_group_incompatible=["alcohol", "carboxylic_acid", "primary_amine"],
+    mechanism="Grignard reagent adds to the aldehyde carbonyl; aqueous acid workup yields a secondary alcohol.",
+    reverse_transform="Disconnect C-C bond alpha to the OH; one fragment becomes RMgBr, the other becomes aldehyde.",
+    safety_notes="Grignard reagents are pyrophoric in air. Strict anhydrous conditions.",
+)
+
+_t(
+    name="Grignard addition to ketone",
+    named_reaction="Grignard reaction",
+    category=ReactionCategory.COUPLING,
+    reagents=["RMgBr"],
+    solvents=["THF", "Et2O"],
+    temperature_range=(-20.0, 25.0),
+    typical_yield=(65.0, 90.0),
+    functional_group_required=["ketone"],
+    functional_group_produced=["alcohol"],
+    functional_group_incompatible=["alcohol", "carboxylic_acid", "primary_amine"],
+    mechanism="Grignard reagent adds to the ketone carbonyl; aqueous acid workup gives a tertiary alcohol.",
+    reverse_transform="Disconnect one of the three C-C bonds at the tertiary alcohol carbon.",
+)
+
+_t(
+    name="Grignard addition to ester (gives tertiary alcohol)",
+    named_reaction="Grignard reaction (2 equiv on ester)",
+    category=ReactionCategory.COUPLING,
+    reagents=["RMgBr (2 equiv)"],
+    solvents=["THF"],
+    temperature_range=(-20.0, 25.0),
+    typical_yield=(60.0, 85.0),
+    functional_group_required=["ester"],
+    functional_group_produced=["alcohol"],
+    functional_group_incompatible=["alcohol", "primary_amine"],
+    mechanism="First equivalent of RMgBr attacks the ester; the tetrahedral intermediate collapses to a ketone + alkoxide. Second equivalent adds to the ketone to give a tertiary alcohol.",
+    reverse_transform="Disconnect two identical R groups from the tertiary alcohol; one fragment is RMgBr, the other is the ester.",
+)
+
+_t(
+    name="Grignard with CO2 (carboxylation)",
+    named_reaction="Grignard carboxylation",
+    category=ReactionCategory.COUPLING,
+    reagents=["RMgBr", "CO2 (dry ice)"],
+    solvents=["THF", "Et2O"],
+    temperature_range=(-78.0, 0.0),
+    typical_yield=(65.0, 90.0),
+    functional_group_required=[],
+    functional_group_produced=["carboxylic_acid"],
+    functional_group_incompatible=["alcohol", "primary_amine", "carboxylic_acid"],
+    mechanism="Grignard nucleophile attacks CO2 to form a carboxylate; acidic workup gives the carboxylic acid with one extra carbon.",
+    reverse_transform="Disconnect the C-COOH bond; carbon fragment becomes RMgBr.",
+)
+
+_t(
+    name="Suzuki coupling",
+    named_reaction="Suzuki-Miyaura coupling",
+    category=ReactionCategory.COUPLING,
+    reagents=["ArB(OH)2 (boronic acid)", "base (K2CO3, Cs2CO3, K3PO4)"],
+    solvents=["THF/water", "dioxane/water", "DMF"],
+    catalysts=["Pd(PPh3)4", "PdCl2(dppf)", "Pd(OAc)2/SPhos"],
+    temperature_range=(60.0, 100.0),
+    typical_yield=(70.0, 95.0),
+    functional_group_required=["alkyl_halide_br", "alkyl_halide_i"],
+    functional_group_produced=[],
+    functional_group_incompatible=[],
+    mechanism="Pd(0) oxidatively adds to the aryl/vinyl halide; transmetalation with the boronate ester transfers the second partner; reductive elimination forms the new C-C bond.",
+    reverse_transform="Disconnect the biaryl C-C bond; one fragment gets halide, the other gets B(OH)2.",
+    safety_notes="Pd catalysts are expensive. Boronic acids are generally low toxicity.",
+)
+
+_t(
+    name="Heck reaction",
+    named_reaction="Heck reaction",
+    category=ReactionCategory.COUPLING,
+    reagents=["aryl/vinyl halide", "alkene", "Et3N (or DIPEA)"],
+    solvents=["DMF", "MeCN", "toluene"],
+    catalysts=["Pd(OAc)2", "Pd(PPh3)4"],
+    temperature_range=(80.0, 140.0),
+    typical_yield=(60.0, 90.0),
+    functional_group_required=["alkene", "alkyl_halide_br"],
+    functional_group_produced=["alkene"],
+    functional_group_incompatible=[],
+    mechanism="Pd(0) oxidatively adds to the halide; syn migratory insertion into the alkene followed by beta-hydride elimination gives a new substituted alkene with retention of the double bond.",
+    reverse_transform="Disconnect the vinylic C-C bond; one fragment gets halide.",
+)
+
+_t(
+    name="Sonogashira coupling",
+    named_reaction="Sonogashira coupling",
+    category=ReactionCategory.COUPLING,
+    reagents=["terminal alkyne", "aryl/vinyl halide", "Et3N (or DIPEA)"],
+    solvents=["THF", "DMF", "Et3N (as solvent)"],
+    catalysts=["Pd(PPh3)4 (or PdCl2(PPh3)2)", "CuI"],
+    temperature_range=(25.0, 80.0),
+    typical_yield=(65.0, 90.0),
+    functional_group_required=["alkyne", "alkyl_halide_br"],
+    functional_group_produced=["alkyne"],
+    functional_group_incompatible=[],
+    mechanism="Cu(I) generates a copper acetylide from the terminal alkyne; Pd(0) oxidatively adds to the halide; transmetalation and reductive elimination form the new C(sp)-C(sp2) bond.",
+    reverse_transform="Disconnect the C(sp)-C(sp2) bond; one fragment gets halide, the other is a terminal alkyne.",
+)
+
+_t(
+    name="Wittig reaction",
+    named_reaction="Wittig reaction",
+    category=ReactionCategory.COUPLING,
+    reagents=["Ph3P=CHR (Wittig ylide)", "n-BuLi (for ylide generation)"],
+    solvents=["THF"],
+    temperature_range=(-78.0, 25.0),
+    typical_yield=(55.0, 85.0),
+    functional_group_required=["aldehyde", "ketone"],
+    functional_group_produced=["alkene"],
+    functional_group_incompatible=[],
+    mechanism="Phosphorus ylide attacks the carbonyl; a betaine forms and closes to an oxaphosphetane, which undergoes retro-[2+2] to give the alkene and Ph3P=O.",
+    reverse_transform="Disconnect the C=C bond; one fragment becomes an aldehyde/ketone, the other becomes a phosphonium salt.",
+    safety_notes="n-BuLi is pyrophoric. Ph3P=O is a troublesome byproduct (hard to remove).",
+)
+
+_t(
+    name="Horner-Wadsworth-Emmons reaction",
+    named_reaction="Horner-Wadsworth-Emmons",
+    category=ReactionCategory.COUPLING,
+    reagents=["(EtO)2P(O)CHR'CO2Et", "NaH (or LDA)"],
+    solvents=["THF"],
+    temperature_range=(-78.0, 25.0),
+    typical_yield=(60.0, 90.0),
+    functional_group_required=["aldehyde", "ketone"],
+    functional_group_produced=["alkene"],
+    functional_group_incompatible=[],
+    mechanism="Stabilised phosphonate carbanion attacks the carbonyl; the resulting betaine cyclises and fragments (retro-[2+2]) to give predominantly the E-alkene and water-soluble diethylphosphate.",
+    reverse_transform="Disconnect the C=C; one fragment becomes aldehyde/ketone, the other a phosphonate ester.",
+)
+
+_t(
+    name="Aldol reaction",
+    named_reaction="Aldol reaction",
+    category=ReactionCategory.COUPLING,
+    reagents=["LDA (for enolate formation)"],
+    solvents=["THF"],
+    temperature_range=(-78.0, 0.0),
+    typical_yield=(60.0, 85.0),
+    functional_group_required=["aldehyde", "ketone"],
+    functional_group_produced=["alcohol", "ketone"],
+    functional_group_incompatible=[],
+    mechanism="Base generates an enolate from one carbonyl; the enolate attacks a second carbonyl to form a beta-hydroxy carbonyl (aldol product). Heating can drive dehydration to the enone.",
+    reverse_transform="Disconnect the C-C bond between the alpha and beta carbons of the beta-hydroxy carbonyl; both fragments are carbonyls.",
+)
+
+_t(
+    name="Claisen condensation",
+    named_reaction="Claisen condensation",
+    category=ReactionCategory.COUPLING,
+    reagents=["NaOEt"],
+    solvents=["EtOH"],
+    temperature_range=(25.0, 80.0),
+    typical_yield=(50.0, 75.0),
+    functional_group_required=["ester"],
+    functional_group_produced=["ester", "ketone"],
+    functional_group_incompatible=[],
+    mechanism="Ethoxide deprotonates the ester alpha-position; the resulting enolate attacks a second ester molecule. Loss of ethoxide gives a beta-keto ester.",
+    reverse_transform="Disconnect the C-C bond alpha to the ketone; both fragments become esters.",
+)
+
+_t(
+    name="Stille coupling",
+    named_reaction="Stille coupling",
+    category=ReactionCategory.COUPLING,
+    reagents=["R-SnBu3 (organostannane)", "aryl/vinyl halide"],
+    solvents=["DMF", "toluene", "THF"],
+    catalysts=["Pd(PPh3)4", "PdCl2(PPh3)2"],
+    temperature_range=(60.0, 110.0),
+    typical_yield=(60.0, 90.0),
+    functional_group_required=["alkyl_halide_br", "alkyl_halide_i"],
+    functional_group_produced=[],
+    functional_group_incompatible=[],
+    mechanism="Pd(0) oxidatively adds to the halide; transmetalation with the stannane transfers R; reductive elimination forms the new C-C bond.",
+    reverse_transform="Disconnect the newly formed C-C bond; one fragment gets halide, the other gets SnBu3.",
+    safety_notes="Organotin compounds are highly toxic (H301/H311/H331, H360, H372). Use with extreme care and proper waste disposal.",
+)
+
+_t(
+    name="Negishi coupling",
+    named_reaction="Negishi coupling",
+    category=ReactionCategory.COUPLING,
+    reagents=["RZnX (organozinc)", "aryl/vinyl halide"],
+    solvents=["THF"],
+    catalysts=["Pd(PPh3)4", "PdCl2(dppf)"],
+    temperature_range=(0.0, 60.0),
+    typical_yield=(65.0, 90.0),
+    functional_group_required=["alkyl_halide_br", "alkyl_halide_i"],
+    functional_group_produced=[],
+    functional_group_incompatible=[],
+    mechanism="Pd(0) oxidatively adds to the halide; transmetalation with the organozinc transfers R; reductive elimination forms the C-C bond. High functional group tolerance.",
+    reverse_transform="Disconnect the C-C bond; one fragment gets halide, the other gets ZnX.",
+)
+
+# -----------------------------------------------------------------
+#  CARBONYL CHEMISTRY  (~10)
+# -----------------------------------------------------------------
+
+_t(
+    name="Fischer esterification",
+    named_reaction="Fischer esterification",
+    category=ReactionCategory.CARBONYL,
+    reagents=["alcohol", "H2SO4 (cat.)"],
+    solvents=["neat", "toluene (Dean-Stark)"],
+    temperature_range=(60.0, 120.0),
+    typical_yield=(50.0, 85.0),
+    functional_group_required=["carboxylic_acid", "alcohol"],
+    functional_group_produced=["ester"],
+    functional_group_incompatible=["primary_amine"],
+    mechanism="Acid-catalysed nucleophilic addition-elimination: protonation of C=O, attack by alcohol, loss of water. Equilibrium driven by excess alcohol or water removal.",
+    reverse_transform="Disconnect the ester bond; fragments are carboxylic acid + alcohol.",
+)
+
+_t(
+    name="Amide formation from acyl chloride and amine",
+    named_reaction="Schotten-Baumann acylation",
+    category=ReactionCategory.CARBONYL,
+    reagents=["RCOCl (acyl chloride)", "Et3N (base)"],
+    solvents=["DCM", "THF"],
+    temperature_range=(0.0, 25.0),
+    typical_yield=(75.0, 95.0),
+    functional_group_required=["primary_amine", "secondary_amine"],
+    functional_group_produced=["amide"],
+    functional_group_incompatible=["alcohol"],
+    mechanism="Nucleophilic amine attacks the acyl chloride; loss of HCl (scavenged by Et3N) gives the amide.",
+    reverse_transform="Disconnect the amide C-N bond; one fragment becomes acyl chloride, the other the amine.",
+)
+
+_t(
+    name="Claisen rearrangement",
+    named_reaction="Claisen rearrangement",
+    category=ReactionCategory.CARBONYL,
+    reagents=[],
+    solvents=["toluene", "decalin", "neat"],
+    temperature_range=(150.0, 250.0),
+    typical_yield=(60.0, 90.0),
+    functional_group_required=["ether", "alkene"],
+    functional_group_produced=["aldehyde", "ketone"],
+    functional_group_incompatible=[],
+    mechanism="Allyl vinyl ether undergoes a concerted [3,3]-sigmatropic rearrangement through a chair-like transition state to give a gamma,delta-unsaturated carbonyl.",
+    reverse_transform="Reconnect the sigma bond as the allyl vinyl ether.",
+)
+
+_t(
+    name="Diels-Alder reaction",
+    named_reaction="Diels-Alder",
+    category=ReactionCategory.CARBONYL,
+    reagents=["diene", "dienophile"],
+    solvents=["toluene", "DCM", "neat"],
+    temperature_range=(25.0, 200.0),
+    typical_yield=(60.0, 95.0),
+    functional_group_required=["alkene"],
+    functional_group_produced=["alkene"],
+    functional_group_incompatible=[],
+    mechanism="Concerted [4+2] cycloaddition between a conjugated diene (s-cis conformation) and a dienophile. Suprafacial on both components; endo rule favours kinetic product.",
+    reverse_transform="Retro-Diels-Alder: disconnect the cyclohexene ring into diene + dienophile.",
+)
+
+_t(
+    name="Beckmann rearrangement",
+    named_reaction="Beckmann rearrangement",
+    category=ReactionCategory.CARBONYL,
+    reagents=["hydroxylamine (to form oxime)", "H2SO4 (or PCl5, SOCl2)"],
+    solvents=["AcOH", "DCM"],
+    temperature_range=(25.0, 130.0),
+    typical_yield=(55.0, 85.0),
+    functional_group_required=["ketone"],
+    functional_group_produced=["amide"],
+    functional_group_incompatible=["primary_amine"],
+    mechanism="Ketoxime undergoes acid-catalysed 1,2-shift of the group anti to the departing hydroxyl; nitrilium ion is captured by water to give the amide (lactam for cyclic ketones).",
+    reverse_transform="Disconnect the amide C-N bond; recombine as ketone.",
+)
+
+_t(
+    name="Cannizzaro reaction",
+    named_reaction="Cannizzaro reaction",
+    category=ReactionCategory.CARBONYL,
+    reagents=["NaOH (conc.)"],
+    solvents=["water"],
+    temperature_range=(25.0, 80.0),
+    typical_yield=(40.0, 50.0),
+    functional_group_required=["aldehyde"],
+    functional_group_produced=["alcohol", "carboxylic_acid"],
+    functional_group_incompatible=[],
+    mechanism="In concentrated base, an aldehyde without alpha-hydrogens disproportionates: one molecule is oxidised to the carboxylate, the other is reduced to the alcohol.",
+    reverse_transform="Combine a primary alcohol and a carboxylic acid derived from the same aldehyde.",
+)
+
+_t(
+    name="Tischenko reaction",
+    named_reaction="Tischenko reaction",
+    category=ReactionCategory.CARBONYL,
+    reagents=["Al(OEt)3 (cat.)"],
+    solvents=["neat", "toluene"],
+    catalysts=["Al(OEt)3"],
+    temperature_range=(0.0, 80.0),
+    typical_yield=(60.0, 90.0),
+    functional_group_required=["aldehyde"],
+    functional_group_produced=["ester"],
+    functional_group_incompatible=[],
+    mechanism="Lewis acid-catalysed disproportionation of two aldehyde molecules: one is oxidised and one is reduced, joined as an ester. Related to Cannizzaro but gives the ester directly.",
+    reverse_transform="Hydrolyse the ester; both fragments derive from the same aldehyde.",
+)
+
+_t(
+    name="Michael addition",
+    named_reaction="Michael addition",
+    category=ReactionCategory.CARBONYL,
+    reagents=["NaOEt (or LDA)"],
+    solvents=["EtOH", "THF"],
+    temperature_range=(-78.0, 25.0),
+    typical_yield=(60.0, 90.0),
+    functional_group_required=["alkene", "ketone"],
+    functional_group_produced=["ketone"],
+    functional_group_incompatible=[],
+    mechanism="A stabilised nucleophile (enolate, malonate, etc.) adds in a 1,4-fashion to an alpha,beta-unsaturated carbonyl (Michael acceptor).",
+    reverse_transform="Disconnect the C-C bond beta to the carbonyl; one fragment is the enolate donor, the other the enone.",
+)
+
+_t(
+    name="Robinson annulation",
+    named_reaction="Robinson annulation",
+    category=ReactionCategory.CARBONYL,
+    reagents=["NaOEt", "methyl vinyl ketone"],
+    solvents=["EtOH", "THF"],
+    temperature_range=(25.0, 80.0),
+    typical_yield=(45.0, 75.0),
+    functional_group_required=["ketone"],
+    functional_group_produced=["ketone", "alkene"],
+    functional_group_incompatible=[],
+    mechanism="Michael addition of a ketone enolate to methyl vinyl ketone, followed by intramolecular aldol condensation and dehydration to form a cyclohexenone ring.",
+    reverse_transform="Disconnect the cyclohexenone ring into a 1,5-diketone, then further into the ketone + MVK.",
+)
+
+_t(
+    name="Baeyer-Villiger oxidation (carbonyl section)",
+    named_reaction="Baeyer-Villiger oxidation",
+    category=ReactionCategory.CARBONYL,
+    reagents=["mCPBA"],
+    solvents=["DCM"],
+    temperature_range=(0.0, 40.0),
+    typical_yield=(60.0, 90.0),
+    functional_group_required=["ketone"],
+    functional_group_produced=["ester"],
+    functional_group_incompatible=["primary_amine"],
+    mechanism="Peracid attacks the ketone; Criegee intermediate undergoes 1,2-alkyl migration (migratory aptitude: tert > sec > aryl > pri > methyl) to insert oxygen.",
+    reverse_transform="Disconnect the ester oxygen; recombine as ketone.",
+)
+
+# -----------------------------------------------------------------
+#  PROTECTION  (~8)
+# -----------------------------------------------------------------
+
+_t(
+    name="Boc protection of amine",
+    named_reaction="Boc protection",
+    category=ReactionCategory.PROTECTION,
+    reagents=["Boc2O", "Et3N (or NaOH)"],
+    solvents=["DCM", "THF", "water/dioxane"],
+    temperature_range=(0.0, 25.0),
+    typical_yield=(85.0, 98.0),
+    functional_group_required=["primary_amine", "secondary_amine"],
+    functional_group_produced=["carbamate"],
+    functional_group_incompatible=[],
+    mechanism="Nucleophilic amine attacks the electrophilic carbonyl of Boc2O; loss of tert-butoxide/CO2 gives the Boc-carbamate.",
+    reverse_transform="Remove Boc with TFA or HCl in dioxane.",
+)
+
+_t(
+    name="Boc deprotection",
+    named_reaction="Boc deprotection",
+    category=ReactionCategory.DEPROTECTION,
+    reagents=["TFA (or HCl in dioxane)"],
+    solvents=["DCM"],
+    temperature_range=(0.0, 25.0),
+    typical_yield=(90.0, 99.0),
+    functional_group_required=["carbamate"],
+    functional_group_produced=["primary_amine", "secondary_amine"],
+    functional_group_incompatible=[],
+    mechanism="Acid protonates the carbamate oxygen; tert-butyl cation departs, generating CO2 and the free amine.",
+    reverse_transform="Protect amine with Boc2O.",
+)
+
+_t(
+    name="Fmoc protection of amine",
+    named_reaction="Fmoc protection",
+    category=ReactionCategory.PROTECTION,
+    reagents=["FmocCl (or Fmoc-OSu)", "Na2CO3 (or NaHCO3)"],
+    solvents=["dioxane/water", "THF"],
+    temperature_range=(0.0, 25.0),
+    typical_yield=(80.0, 95.0),
+    functional_group_required=["primary_amine", "secondary_amine"],
+    functional_group_produced=["carbamate"],
+    functional_group_incompatible=[],
+    mechanism="Amine attacks FmocCl, displacing chloride; base scavenges HCl.",
+    reverse_transform="Remove Fmoc with piperidine (20% in DMF).",
+)
+
+_t(
+    name="Fmoc deprotection",
+    named_reaction="Fmoc deprotection",
+    category=ReactionCategory.DEPROTECTION,
+    reagents=["piperidine (20% in DMF)"],
+    solvents=["DMF"],
+    temperature_range=(20.0, 25.0),
+    typical_yield=(90.0, 99.0),
+    functional_group_required=["carbamate"],
+    functional_group_produced=["primary_amine", "secondary_amine"],
+    functional_group_incompatible=[],
+    mechanism="Piperidine abstracts the acidic fluorenyl proton; beta-elimination releases dibenzofulvene and CO2, liberating the free amine. Piperidine scavenges the dibenzofulvene.",
+    reverse_transform="Protect amine with FmocCl.",
+)
+
+_t(
+    name="TBS protection of alcohol",
+    named_reaction="TBS silylation",
+    category=ReactionCategory.PROTECTION,
+    reagents=["TBSCl", "imidazole"],
+    solvents=["DMF", "DCM"],
+    temperature_range=(0.0, 25.0),
+    typical_yield=(85.0, 98.0),
+    functional_group_required=["alcohol"],
+    functional_group_produced=["silyl_ether"],
+    functional_group_incompatible=[],
+    mechanism="Imidazole acts as nucleophilic catalyst, activating TBSCl; the alcohol then displaces imidazole to form the TBS ether.",
+    reverse_transform="Remove TBS with TBAF in THF.",
+)
+
+_t(
+    name="TBS deprotection",
+    named_reaction="TBS removal",
+    category=ReactionCategory.DEPROTECTION,
+    reagents=["TBAF"],
+    solvents=["THF"],
+    temperature_range=(0.0, 25.0),
+    typical_yield=(90.0, 99.0),
+    functional_group_required=["silyl_ether"],
+    functional_group_produced=["alcohol"],
+    functional_group_incompatible=[],
+    mechanism="Fluoride ion attacks silicon (very strong Si-F bond, 140 kcal/mol), displacing the alkoxide which is protonated on workup.",
+    reverse_transform="Protect alcohol with TBSCl/imidazole.",
+)
+
+_t(
+    name="Benzyl protection of alcohol",
+    named_reaction="Benzyl protection",
+    category=ReactionCategory.PROTECTION,
+    reagents=["BnBr", "NaH"],
+    solvents=["DMF", "THF"],
+    temperature_range=(0.0, 25.0),
+    typical_yield=(80.0, 95.0),
+    functional_group_required=["alcohol"],
+    functional_group_produced=["ether"],
+    functional_group_incompatible=["alkyl_halide"],
+    mechanism="NaH deprotonates the alcohol; the alkoxide displaces bromide from BnBr in an SN2 reaction.",
+    reverse_transform="Remove Bn by hydrogenolysis (H2/Pd-C).",
+)
+
+_t(
+    name="Benzyl deprotection (hydrogenolysis)",
+    named_reaction="Hydrogenolysis",
+    category=ReactionCategory.DEPROTECTION,
+    reagents=["H2", "Pd/C"],
+    solvents=["EtOAc", "MeOH", "EtOH"],
+    catalysts=["Pd/C"],
+    temperature_range=(20.0, 40.0),
+    typical_yield=(85.0, 99.0),
+    functional_group_required=["ether"],
+    functional_group_produced=["alcohol"],
+    functional_group_incompatible=["alkene", "alkyne"],
+    mechanism="Pd-catalysed hydrogenolysis cleaves the benzylic C-O bond. Toluene is released as byproduct.",
+    reverse_transform="Protect alcohol with BnBr/NaH.",
+    safety_notes="H2/Pd-C: flammable gas + pyrophoric catalyst. Filter Pd/C through Celite before discarding.",
+)
+
+_t(
+    name="Acetyl protection of alcohol",
+    named_reaction="Acetylation",
+    category=ReactionCategory.PROTECTION,
+    reagents=["Ac2O", "Et3N (or pyridine)", "DMAP (cat.)"],
+    solvents=["DCM"],
+    catalysts=["DMAP"],
+    temperature_range=(0.0, 25.0),
+    typical_yield=(85.0, 98.0),
+    functional_group_required=["alcohol"],
+    functional_group_produced=["ester"],
+    functional_group_incompatible=["primary_amine"],
+    mechanism="DMAP-catalysed nucleophilic acyl substitution: DMAP activates acetic anhydride, the alcohol attacks, and acetic acid departs.",
+    reverse_transform="Remove acetyl with K2CO3/MeOH or LiOH/THF-water.",
+)
+
+_t(
+    name="PMB protection of alcohol",
+    named_reaction="PMB protection",
+    category=ReactionCategory.PROTECTION,
+    reagents=["PMBCl", "NaH"],
+    solvents=["DMF", "THF"],
+    temperature_range=(0.0, 25.0),
+    typical_yield=(75.0, 90.0),
+    functional_group_required=["alcohol"],
+    functional_group_produced=["ether"],
+    functional_group_incompatible=[],
+    mechanism="NaH deprotonates alcohol; the alkoxide displaces chloride from PMBCl in an SN2 reaction.",
+    reverse_transform="Remove PMB with DDQ (oxidative) or TFA/anisole (acidic).",
+)
+
+_t(
+    name="PMB deprotection with DDQ",
+    named_reaction="PMB deprotection",
+    category=ReactionCategory.DEPROTECTION,
+    reagents=["DDQ"],
+    solvents=["DCM/water", "DCM/pH 7 buffer"],
+    temperature_range=(0.0, 25.0),
+    typical_yield=(75.0, 95.0),
+    functional_group_required=["ether"],
+    functional_group_produced=["alcohol"],
+    functional_group_incompatible=["alkene"],
+    mechanism="DDQ oxidises the electron-rich PMB group to a quinone methide/oxocarbenium species; water (or buffer) traps it, releasing the free alcohol.",
+    reverse_transform="Protect with PMBCl/NaH.",
+)
+
+_t(
+    name="Acetonide protection of 1,2-diol",
+    named_reaction="Acetonide protection",
+    category=ReactionCategory.PROTECTION,
+    reagents=["2,2-dimethoxypropane", "p-TsOH (cat.)"],
+    solvents=["acetone", "DMF"],
+    catalysts=["p-TsOH"],
+    temperature_range=(20.0, 50.0),
+    typical_yield=(80.0, 95.0),
+    functional_group_required=["diol"],
+    functional_group_produced=["acetal"],
+    functional_group_incompatible=[],
+    mechanism="Acid-catalysed transacetalisation: the diol displaces methanol from 2,2-dimethoxypropane to form a cyclic acetonide.",
+    reverse_transform="Remove acetonide with aqueous acid (pTsOH/MeOH or AcOH/water).",
+)
+
+_t(
+    name="THP protection of alcohol",
+    named_reaction="THP protection",
+    category=ReactionCategory.PROTECTION,
+    reagents=["DHP (3,4-dihydro-2H-pyran)", "p-TsOH (cat.)"],
+    solvents=["DCM"],
+    catalysts=["p-TsOH"],
+    temperature_range=(0.0, 25.0),
+    typical_yield=(80.0, 95.0),
+    functional_group_required=["alcohol"],
+    functional_group_produced=["acetal"],
+    functional_group_incompatible=[],
+    mechanism="Acid-catalysed addition of the alcohol to the vinyl ether of DHP forms a mixed THP acetal. Note: creates a new stereocenter.",
+    reverse_transform="Remove THP with p-TsOH in MeOH or PPTS in EtOH.",
+)
+
+# -----------------------------------------------------------------
+#  REARRANGEMENT  (~6)
+# -----------------------------------------------------------------
+
+_t(
+    name="Cope rearrangement",
+    named_reaction="Cope rearrangement",
+    category=ReactionCategory.REARRANGEMENT,
+    reagents=[],
+    solvents=["toluene", "decalin"],
+    temperature_range=(150.0, 300.0),
+    typical_yield=(50.0, 85.0),
+    functional_group_required=["alkene"],
+    functional_group_produced=["alkene"],
+    functional_group_incompatible=[],
+    mechanism="[3,3]-Sigmatropic rearrangement of a 1,5-diene through a chair-like transition state. Oxy-Cope variant (3-hydroxy-1,5-diene) is driven by tautomerisation to a ketone.",
+    reverse_transform="Reverse [3,3] shift.",
+)
+
+_t(
+    name="Pinacol rearrangement",
+    named_reaction="Pinacol rearrangement",
+    category=ReactionCategory.REARRANGEMENT,
+    reagents=["H2SO4"],
+    solvents=["water"],
+    temperature_range=(25.0, 100.0),
+    typical_yield=(55.0, 80.0),
+    functional_group_required=["diol"],
+    functional_group_produced=["ketone"],
+    functional_group_incompatible=[],
+    mechanism="Acid protonates one hydroxyl; water departs to give a carbocation; 1,2-alkyl shift to the cationic centre, followed by loss of a proton gives pinacolone (a ketone).",
+    reverse_transform="Add two OH groups to the ketone alpha-carbon.",
+)
+
+_t(
+    name="Curtius rearrangement",
+    named_reaction="Curtius rearrangement",
+    category=ReactionCategory.REARRANGEMENT,
+    reagents=["DPPA (diphenylphosphoryl azide)", "Et3N"],
+    solvents=["toluene", "THF"],
+    temperature_range=(60.0, 110.0),
+    typical_yield=(60.0, 85.0),
+    functional_group_required=["carboxylic_acid"],
+    functional_group_produced=["primary_amine", "carbamate"],
+    functional_group_incompatible=[],
+    mechanism="Carboxylic acid is converted to the acyl azide; thermolysis induces 1,2-shift with loss of N2 to give an isocyanate. Trapping with water gives the amine (one fewer carbon); trapping with alcohol gives a carbamate.",
+    reverse_transform="Amine + CO2 -> carboxylic acid (formal).",
+    safety_notes="Acyl azides are potentially explosive. DPPA generates HN3 (toxic).",
+)
+
+_t(
+    name="Hofmann rearrangement",
+    named_reaction="Hofmann rearrangement",
+    category=ReactionCategory.REARRANGEMENT,
+    reagents=["NaOH", "Br2"],
+    solvents=["water"],
+    temperature_range=(0.0, 70.0),
+    typical_yield=(55.0, 80.0),
+    functional_group_required=["amide"],
+    functional_group_produced=["primary_amine"],
+    functional_group_incompatible=[],
+    mechanism="Bromination of the amide nitrogen, base-induced 1,2-shift with loss of bromide gives an isocyanate, which is hydrolysed to the amine (one fewer carbon).",
+    reverse_transform="Amine + CO -> amide (formal).",
+)
+
+
+# -----------------------------------------------------------------
+#  MISCELLANEOUS  (~4)
+# -----------------------------------------------------------------
+
+_t(
+    name="Appel reaction (alcohol to alkyl halide)",
+    named_reaction="Appel reaction",
+    category=ReactionCategory.MISC,
+    reagents=["PPh3", "CCl4 (or CBr4, or I2)"],
+    solvents=["DCM"],
+    temperature_range=(0.0, 25.0),
+    typical_yield=(70.0, 95.0),
+    functional_group_required=["alcohol"],
+    functional_group_produced=["alkyl_halide"],
+    functional_group_incompatible=["carboxylic_acid"],
+    mechanism=(
+        "PPh3 reacts with CCl4 to form a phosphonium salt; the alcohol oxygen "
+        "attacks phosphorus, forming an oxyphosphonium intermediate. Chloride "
+        "displaces the activated oxygen via SN2 with inversion."
+    ),
+    reverse_transform="Disconnect C-X; replace halide with hydroxyl.",
+    safety_notes="CCl4 is toxic and an ozone depleter. CBr4 is preferred where possible.",
+)
+
+_t(
+    name="Staudinger reduction (azide to amine)",
+    named_reaction="Staudinger reduction",
+    category=ReactionCategory.MISC,
+    reagents=["PPh3", "H2O"],
+    solvents=["THF", "THF/water"],
+    temperature_range=(20.0, 60.0),
+    typical_yield=(75.0, 95.0),
+    functional_group_required=["azide"],
+    functional_group_produced=["primary_amine"],
+    functional_group_incompatible=[],
+    mechanism=(
+        "PPh3 attacks the terminal nitrogen of the azide, releasing N2 and "
+        "forming an iminophosphorane (aza-ylide). Hydrolysis gives the "
+        "primary amine and Ph3P=O."
+    ),
+    reverse_transform="Convert amine back to azide via diazotransfer.",
+    safety_notes="Organic azides can be shock-sensitive. Ph3P=O byproduct.",
+)
+
+_t(
+    name="Corey-Chaykovsky epoxidation / cyclopropanation",
+    named_reaction="Corey-Chaykovsky reaction",
+    category=ReactionCategory.MISC,
+    reagents=["trimethylsulfonium iodide (or trimethylsulfoxonium iodide)", "NaH"],
+    solvents=["DMSO", "THF"],
+    temperature_range=(0.0, 25.0),
+    typical_yield=(55.0, 80.0),
+    functional_group_required=["aldehyde", "ketone"],
+    functional_group_produced=["epoxide", "cyclopropane"],
+    functional_group_incompatible=[],
+    mechanism=(
+        "Deprotonation of the sulfonium salt gives the sulfur ylide, which "
+        "attacks the carbonyl. With the sulfonium ylide, the betaine closes "
+        "to an epoxide; with the sulfoxonium ylide, cyclopropanation of enones "
+        "occurs via conjugate addition then ring closure."
+    ),
+    reverse_transform="Open the epoxide to retrieve the carbonyl; or open the cyclopropane.",
+    safety_notes="NaH is pyrophoric. Handle under inert atmosphere.",
+)
+
+_t(
+    name="Olefin metathesis (ring-closing)",
+    named_reaction="Ring-closing metathesis (RCM)",
+    category=ReactionCategory.MISC,
+    reagents=["Grubbs 2nd generation catalyst"],
+    solvents=["DCM", "toluene"],
+    catalysts=["Grubbs 2nd generation"],
+    temperature_range=(25.0, 40.0),
+    typical_yield=(60.0, 90.0),
+    functional_group_required=["alkene"],
+    functional_group_produced=["alkene"],
+    functional_group_incompatible=["thiol", "primary_amine"],
+    mechanism=(
+        "Ruthenium carbene catalyst initiates by [2+2] cycloaddition with one "
+        "terminal alkene; metallacyclobutane fragmentation releases ethylene. "
+        "Intramolecular [2+2] with the second alkene closes the ring."
+    ),
+    reverse_transform="Open the ring by cross-metathesis; restore two terminal alkenes.",
+    safety_notes="Grubbs catalysts are air-sensitive. Ethylene gas is evolved.",
+)
+
+# -----------------------------------------------------------------
+#  METATHESIS / C-H ACTIVATION / ASYMMETRIC  (~5)
+# -----------------------------------------------------------------
+
+_t(
+    name="Cross-metathesis (Grubbs catalyst)",
+    named_reaction="Cross-metathesis",
+    category=ReactionCategory.MISC,
+    reagents=["Grubbs 2nd generation catalyst", "terminal alkene partner"],
+    solvents=["DCM", "toluene"],
+    catalysts=["Grubbs 2nd generation"],
+    temperature_range=(25.0, 45.0),
+    typical_yield=(40.0, 80.0),
+    functional_group_required=["alkene"],
+    functional_group_produced=["alkene"],
+    functional_group_incompatible=["thiol", "primary_amine"],
+    mechanism=(
+        "Ruthenium carbene initiates by [2+2] cycloaddition with one "
+        "terminal olefin; metallacyclobutane fragmentation and re-entry "
+        "with the cross-partner olefin produces the hetero-disubstituted "
+        "alkene. Statistical mixtures are minimised by choosing partners "
+        "of different reactivity types (Type I / Type II / Type III)."
+    ),
+    reverse_transform=(
+        "Disconnect the internal alkene; each fragment becomes a "
+        "terminal olefin."
+    ),
+    scale_notes=(
+        "Catalyst loading typically 1-5 mol%. Ethylene removal by "
+        "sparging or reduced pressure shifts equilibrium toward product."
+    ),
+    safety_notes=(
+        "Grubbs catalysts are air-sensitive. Ethylene gas is evolved; "
+        "ensure adequate ventilation."
+    ),
+)
+
+_t(
+    name="Pd-catalysed C-H activation (arene functionalisation)",
+    named_reaction="Pd-catalysed C-H activation",
+    category=ReactionCategory.COUPLING,
+    reagents=["aryl halide (or oxidant)", "PivOH (or AcOH)"],
+    solvents=["DMA", "toluene", "DMF"],
+    catalysts=["Pd(OAc)2"],
+    temperature_range=(80.0, 140.0),
+    typical_yield=(30.0, 75.0),
+    functional_group_required=["aromatic_ring"],
+    functional_group_produced=["aromatic_ring"],
+    functional_group_incompatible=["thiol"],
+    mechanism=(
+        "Pd(II) coordinates to the arene and undergoes concerted "
+        "metalation-deprotonation (CMD) at the least hindered C-H bond, "
+        "assisted by carboxylate base. The resulting aryl-Pd species "
+        "either undergoes oxidative Heck-type coupling or is oxidised "
+        "to Pd(IV) before reductive elimination to form the new C-C bond."
+    ),
+    reverse_transform=(
+        "Disconnect the newly formed aryl-aryl or aryl-R bond; "
+        "one fragment keeps H, the other gets a halide or equivalent."
+    ),
+    scale_notes=(
+        "Regioselectivity is substrate-dependent; directing groups "
+        "(pyridine, amide, oxazoline) greatly improve selectivity. "
+        "Typical Pd loading 5-10 mol%."
+    ),
+    safety_notes=(
+        "Pd(OAc)2 is a skin sensitiser. DMA is a reproductive toxin "
+        "(H360). High temperatures require pressure-rated equipment."
+    ),
+)
+
+_t(
+    name="Asymmetric hydrogenation (Rh or Ru catalysed)",
+    named_reaction="Asymmetric hydrogenation",
+    category=ReactionCategory.REDUCTION,
+    reagents=["H2"],
+    solvents=["MeOH", "iPrOH", "DCM"],
+    catalysts=["Rh(cod)2BF4 / chiral bisphosphine", "Ru(OAc)2(BINAP)"],
+    temperature_range=(20.0, 50.0),
+    typical_yield=(85.0, 99.0),
+    functional_group_required=["alkene"],
+    functional_group_produced=["alkane"],
+    functional_group_incompatible=["thiol"],
+    mechanism=(
+        "Chiral transition-metal complex (Rh or Ru with enantiomerically "
+        "pure bisphosphine ligand) coordinates the prochiral olefin. "
+        "Oxidative addition of H2 followed by migratory insertion and "
+        "reductive elimination delivers H2 across the double bond with "
+        "enantioselectivities typically >95% ee."
+    ),
+    reverse_transform=(
+        "Disconnect two C-H bonds on adjacent carbons; restore the "
+        "alkene with defined geometry."
+    ),
+    scale_notes=(
+        "Highly scalable; used industrially for L-DOPA, menthol, etc. "
+        "Catalyst loadings as low as 0.01 mol% on scale. H2 pressures "
+        "of 1-50 atm are common."
+    ),
+    safety_notes=(
+        "H2 is extremely flammable (H220). Pressure equipment must "
+        "be rated. Chiral ligands are expensive."
+    ),
+)
+
+_t(
+    name="Ring-opening metathesis polymerisation (ROMP)",
+    named_reaction="ROMP",
+    category=ReactionCategory.POLYMERIZATION,
+    reagents=["Grubbs 3rd generation catalyst (or Grubbs 2nd gen)"],
+    solvents=["DCM", "THF", "toluene"],
+    catalysts=["Grubbs 3rd generation"],
+    temperature_range=(20.0, 40.0),
+    typical_yield=(80.0, 99.0),
+    functional_group_required=["alkene"],
+    functional_group_produced=["alkene"],
+    functional_group_incompatible=["thiol", "primary_amine"],
+    mechanism=(
+        "Ruthenium alkylidene initiates by [2+2] cycloaddition with the "
+        "strained cyclic olefin (norbornene, cyclooctene, etc.); "
+        "metallacyclobutane retro-[2+2] opens the ring and regenerates "
+        "the active alkylidene. Repetitive ring-opening of strained "
+        "monomers produces a linear polymer with backbone unsaturation. "
+        "Thermodynamic driving force is the release of ring strain."
+    ),
+    reverse_transform=(
+        "Depolymerise the unsaturated polymer back to cyclic monomer "
+        "under dilute conditions (ring-closing metathesis)."
+    ),
+    scale_notes=(
+        "Living polymerisation: PDI close to 1.0. Control molecular "
+        "weight via monomer-to-initiator ratio. Quench with ethyl "
+        "vinyl ether."
+    ),
+    safety_notes=(
+        "Strained monomers (e.g. dicyclopentadiene) are flammable and "
+        "may self-polymerise. Ru catalysts are air-sensitive."
+    ),
+)
+
+_t(
+    name="Olefin cross-metathesis (selective, with acrylate partner)",
+    named_reaction="Olefin cross-metathesis",
+    category=ReactionCategory.MISC,
+    reagents=["Hoveyda-Grubbs 2nd generation catalyst", "methyl acrylate"],
+    solvents=["DCM", "toluene"],
+    catalysts=["Hoveyda-Grubbs 2nd generation"],
+    temperature_range=(25.0, 50.0),
+    typical_yield=(50.0, 85.0),
+    functional_group_required=["alkene"],
+    functional_group_produced=["alkene", "ester"],
+    functional_group_incompatible=["thiol", "primary_amine"],
+    mechanism=(
+        "Hoveyda-Grubbs catalyst releases the chelating isopropoxy "
+        "styrenyl ligand to generate the active 14-electron Ru "
+        "alkylidene. [2+2] cycloaddition with the Type I olefin "
+        "(terminal alkene) followed by cycloreversion, then a second "
+        "[2+2]/retro-[2+2] cycle with the Type II partner (acrylate) "
+        "gives the E-cross product selectively. Ethylene by-product "
+        "is removed under reduced pressure."
+    ),
+    reverse_transform=(
+        "Disconnect the internal alkene adjacent to the ester; "
+        "one fragment is a terminal olefin, the other is the acrylate."
+    ),
+    scale_notes=(
+        "Hoveyda-Grubbs catalyst is more robust than Grubbs 2nd gen "
+        "for electron-poor partners. Typical loading 2-5 mol%."
+    ),
+    safety_notes=(
+        "Methyl acrylate is a skin sensitiser and respiratory irritant "
+        "(H312/H332). Ru catalysts are air-sensitive."
+    ),
+)
+
+
+# =====================================================================
+#  Lookup helpers
+# =====================================================================
+
+def lookup_by_category(cat: ReactionCategory) -> list[ReactionTemplate]:
+    """Return all templates belonging to *cat*.
+
+    Parameters
+    ----------
+    cat : ReactionCategory
+        The reaction category to filter on.
+
+    Returns
+    -------
+    list[ReactionTemplate]
+        All templates whose ``category`` matches *cat*.
+    """
+    return [r for r in REACTION_TEMPLATES if r.category == cat]
+
+
+def lookup_by_name(name: str) -> list[ReactionTemplate]:
+    """Case-insensitive substring search on template name or named_reaction.
+
+    Parameters
+    ----------
+    name : str
+        Search substring (case-insensitive).
+
+    Returns
+    -------
+    list[ReactionTemplate]
+        Templates whose ``name`` or ``named_reaction`` contains *name*.
+    """
+    q = name.lower()
+    return [r for r in REACTION_TEMPLATES
+            if q in r.name.lower()
+            or (r.named_reaction and q in r.named_reaction.lower())]
+
+
+def lookup_by_functional_group(fg: str) -> list[ReactionTemplate]:
+    """Find reactions that require a given functional group on the substrate.
+
+    Parameters
+    ----------
+    fg : str
+        Functional-group label (case-insensitive), e.g. ``"alcohol"``,
+        ``"alkene"``, ``"ketone"``.
+
+    Returns
+    -------
+    list[ReactionTemplate]
+        Templates whose ``functional_group_required`` list contains *fg*.
+    """
+    q = fg.lower()
+    return [r for r in REACTION_TEMPLATES
+            if q in [f.lower() for f in r.functional_group_required]]
+
+
+def lookup_by_reagent(reagent: str) -> list[ReactionTemplate]:
+    """Find reactions that use a given reagent.
+
+    Performs a case-insensitive substring search across each template's
+    ``reagents`` list.
+
+    Parameters
+    ----------
+    reagent : str
+        Reagent name or fragment (case-insensitive), e.g. ``"NaBH4"``,
+        ``"Pd"``, ``"mCPBA"``.
+
+    Returns
+    -------
+    list[ReactionTemplate]
+        Templates that reference *reagent* in their reagent list.
+    """
+    q = reagent.lower()
+    return [r for r in REACTION_TEMPLATES
+            if any(q in rgt.lower() for rgt in r.reagents)]
+
+
+# ------------------------------------------------------------------
+#  Legacy aliases (backwards compatibility)
+# ------------------------------------------------------------------
+
+def find_reactions_for_fg(fg_name: str) -> list[ReactionTemplate]:
+    """Find reactions that can transform a given functional group.
+
+    .. deprecated:: Use :func:`lookup_by_functional_group` instead.
+    """
+    return lookup_by_functional_group(fg_name)
+
+
+def find_reactions_producing(fg_name: str) -> list[ReactionTemplate]:
+    """Find reactions that produce a given functional group."""
+    q = fg_name.lower()
+    return [r for r in REACTION_TEMPLATES
+            if q in [f.lower() for f in r.functional_group_produced]]
+
+
+def find_reactions_by_category(category: ReactionCategory) -> list[ReactionTemplate]:
+    """Return all templates that belong to *category*.
+
+    .. deprecated:: Use :func:`lookup_by_category` instead.
+    """
+    return lookup_by_category(category)
+
+
+def find_reactions_by_name(query: str) -> list[ReactionTemplate]:
+    """Search templates by name or named-reaction string.
+
+    .. deprecated:: Use :func:`lookup_by_name` instead.
+    """
+    return lookup_by_name(query)