Appendix F — Named Reactions Reference

A dense reference of the named reactions every organic chemist should recognize. Each entry: name (person/year if iconic) — one-line description, transform notation, key reagents, mechanism in 1-3 lines, scope/limits, chapter cross-reference.

Organized alphabetically. A by-transformation cross-index appears at the end.

A

Aldol (1872, Wurtz/Borodin) — enolate + carbonyl → β-hydroxy carbonyl. R-CH₂-C(=O)-R' + R''-CHO → R-CH(C(=O)-R')-CH(OH)-R''. Base (LDA, NaOH) or acid; Zimmerman-Traxler chair TS controls syn/anti. Ch 28.

Aldol condensation — Aldol → dehydration → α,β-unsaturated carbonyl. Forces by extended conjugation. Ch 28.

Appel (1975) — R-OH → R-X using CCl₄/CBr₄ + PPh₃. SN2 on activated phosphonium intermediate; inversion at C. Mild, neutral. Ch 25.

Arndt-Eistert — R-COOH → R-CH₂-COOH (one-carbon homologation) via acyl chloride → diazoketone → Wolff rearrangement. Ch 27.

B

Baeyer-Villiger (1899) — ketone + peracid (mCPBA, TFPAA) → ester. R-C(=O)-R' → R-C(=O)-O-R'. Migration aptitude: H > 3° > 2° aryl > 1° > Me. Retention at migrating C. Ch 36.

Bamberger rearrangement — N-arylhydroxylamines → 4-aminophenols under acid. Industrial classic. Ch 30.

Barton decarboxylation / Barton-McCombie — R-OH → R-H via xanthate + Bu₃SnH/AIBN (radical deoxygenation). Ch 18, 36.

Beckmann rearrangement — ketoxime → amide. R₂C=N-OH + H⁺ → R-C(=O)-NHR'. Anti group migrates to N; conc. acid or SOCl₂. Ch 30.

Bergman cyclization (1972) — enediyne → 1,4-benzenediyl diradical → arene (after H abstraction). Mechanism behind enediyne antitumor antibiotics (calicheamicin). Ch 39.

Birch reduction (1944) — Ar-H + Na/NH₃(l)/ROH → 1,4-cyclohexadiene. Radical anion → protonation → radical anion → protonation. EWG → ipso/para unconjugated diene; EDG → 2,5-unconjugated diene. Ch 21.

Brown hydroboration (Nobel 1979) — alkene + BH₃ (or 9-BBN) → R-BR'₂ → H₂O₂/NaOH → R-OH. Anti-Markovnikov, syn-addition. With chiral boranes (Ipc₂BH): asymmetric. Ch 16.

Buchwald-Hartwig amination (1994) — Pd-catalyzed Ar-X + HNR₂ → Ar-NR₂. Pd(0)/ligand (XPhos, BrettPhos, DavePhos); strong base (NaOt-Bu, Cs₂CO₃). Tolerates aryl chlorides with right ligand. Ch 23, 37.

C

Cannizzaro (1853) — non-enolizable aldehyde + conc. NaOH → 1° alcohol + carboxylate (disproportionation). 2 Ar-CHO → Ar-CH₂OH + Ar-COO⁻. Ch 25.

Carroll rearrangement — allyl β-ketoester → γ,δ-unsat ketone via Claisen + decarboxylation. Ch 39.

Chan-Lam coupling — Ar-B(OH)₂ + HNR₂ → Ar-NR₂ with Cu(OAc)₂, air, room temp. Mild oxidative N-arylation. Ch 37.

Chichibabin — pyridine + NaNH₂ → 2-aminopyridine + H₂. Direct amination of electron-poor azines. Ch 23.

Claisen condensation (1887) — 2 esters → β-ketoester. NaOEt; loses one OR equivalent. Ch 28.

Claisen rearrangement — allyl vinyl ether → γ,δ-unsat carbonyl. [3,3]-sigmatropic, concerted, chair TS, suprafacial-suprafacial. Aza- and aromatic variants. Ch 39.

Clemmensen reduction (1913) — Ar-C(=O)-R + Zn(Hg)/HCl → Ar-CH₂-R. Carbonyl → CH₂; complements Wolff-Kishner (acid- vs base-tolerant). Ch 21, 36.

Cope elimination — R₃N⁺-O⁻ → alkene + R₂NOH via syn periplanar TS at ~150 °C. Ch 12.

Cope rearrangement — 1,5-hexadiene → 1,5-hexadiene ([3,3]-sigmatropic, degenerate without substituents). Oxy-Cope is dramatically accelerated by alkoxide at C3. Ch 39.

Corey-Chaykovsky — sulfur ylide (Me₃S⁺-CH₂⁻ or Me₂S(=O)⁺-CH₂⁻) + carbonyl → epoxide (S-ylide) or cyclopropane (S-O ylide on enone). Ch 25.

Corey-Fuchs — R-CHO → R-C≡CH via R-CH=CBr₂ (CBr₄/PPh₃) → n-BuLi. Aldehyde → one-carbon-longer terminal alkyne. Ch 17.

Corey-Seebach — 1,3-dithiane as acyl anion synthon (umpolung). Deprotonate with n-BuLi → alkylate → hydrolyze to aldehyde or ketone. Ch 29.

Criegee oxidation — see ozonolysis. Criegee intermediate is the carbonyl oxide formed in O₃ cleavage. Ch 16.

Curtius rearrangement — acyl azide → isocyanate + N₂ (concerted, retention at migrating C). Hydrolysis → 1° amine (one C shorter than starting acid). Ch 30.

D

Dakin oxidation — o/p-hydroxyaryl aldehyde + H₂O₂/NaOH → catechol/hydroquinone. Aryl migration analog of Baeyer-Villiger on aldehydes. Ch 36.

Danheiser annulation — TMS-cyclopropene + enone → cyclopentane. Ch 39.

DBU (1,8-diazabicycloundec-7-ene) — strong, non-nucleophilic hindered amine base. pKₐ(BH⁺) ~24 in MeCN. Drives E2/aldol, deprotonates α-CH. Ch 12.

Dess-Martin periodinane (DMP) — 1° OH → CHO; 2° OH → ketone. Mild, room temp, neutral; tolerates acid-sensitive groups. Ch 36.

DIBAL-H (diisobutylaluminum hydride) — at -78 °C: ester → aldehyde (stops at hemiacetal); nitrile → aldehyde. At rt: ester → 1° alcohol. Ch 25, 26.

Dieckmann — intramolecular Claisen. Diester → cyclic β-ketoester. Best for 5- and 6-rings. Ch 28.

Diels-Alder (1928, Nobel 1950) — diene (s-cis) + dienophile → cyclohexene. Concerted [4+2], suprafacial-suprafacial, endo preferred (kinetic). Electron-rich diene + electron-poor dienophile favored (normal demand); inverse demand swaps. Ch 19.

E

Edman degradation — N-terminal residue of a peptide → PTH-amino acid + shortened peptide. Sequencing tool. Ch 38.

Eschweiler-Clarke — 1° or 2° amine + HCHO + HCOOH → N-methylated amine (reductive amination, formate as reductant). Limited to methylation. Ch 30.

Evans aldol (1980s) — chiral oxazolidinone (Evans auxiliary) acylated → enolize (Bu₂BOTf, Et₃N) → aldehyde → highly diastereoselective syn-aldol. Auxiliary cleaved with LiOH/H₂O₂ to give free acid. Ch 28.

F

Favorskii rearrangement — α-halo ketone + base → cyclopropanone intermediate → ring-contracted ester/acid. Useful for ring contraction. Ch 28.

Finkelstein — R-X + NaI in acetone → R-I + NaX↓. Drives by NaCl/NaBr precipitation in acetone. SN2; 1° best. Ch 10.

Fischer esterification — R-COOH + R'-OH + H⁺ ⇌ R-COO-R' + H₂O. Equilibrium; drive with excess alcohol or Dean-Stark water removal. Ch 26.

Fischer indole synthesis — aryl hydrazone + heat/acid → indole. [3,3]-sigmatropic + tautomerizations + NH₃ loss. Ch 23.

Friedländer synthesis — 2-aminobenzaldehyde + ketone → quinoline. Acid- or base-catalyzed. Ch 23.

Friedel-Crafts alkylation — Ar-H + R-X/AlCl₃ → Ar-R. Carbocation EAS; suffers rearrangement and polyalkylation. Ch 21.

Friedel-Crafts acylation — Ar-H + RCOCl/AlCl₃ → Ar-C(=O)R. Acylium EAS; no rearrangement; deactivates ring (no overacylation). Ch 21.

Fukuyama amine synthesis — sulfonamide alkylation (Ns or Ts) → SN2 → deprotect → 2° amine. Mitsunobu-compatible. Ch 30.

G

Gabriel synthesis — K-phthalimide + R-X → N-alkyl phthalimide → hydrazinolysis → R-NH₂ (clean 1° amine). Ch 30.

Glaser coupling — 2 R-C≡C-H + Cu(I)/O₂ → R-C≡C-C≡C-R. Oxidative homocoupling of terminal alkynes. Ch 17, 37.

Grignard reaction — R-MgX + carbonyl → alcohol after workup. R-MgX + RCHO → 2° OH; + R'CO-R'' → 3° OH; + CO₂ → COOH; + ester → 3° OH (2 eq); + nitrile → ketone. Ch 25.

Grubbs metathesis — Ru-alkylidene catalyst (Grubbs I, II, III, Hoveyda-Grubbs II) on alkenes → new alkenes + ethylene. RCM, CM, ROMP variants. Ch 37.

H

Haloform reaction — methyl ketone + 3X₂/NaOH → carboxylate + CHX₃. Iodoform test (yellow CHI₃) for methyl ketones / acetaldehyde / 2° methyl carbinols. Ch 27.

Hantzsch dihydropyridine synthesis — β-ketoester + aldehyde + NH₃ → 1,4-dihydropyridine. Oxidation → pyridine. Multicomponent. Ch 23.

Heck reaction (Nobel 2010) — Pd-cat. Ar-X + alkene → Ar-substituted alkene + HX. Syn-insertion, syn-β-hydride elimination. Ch 37.

Hell-Volhard-Zelinsky (HVZ) — R-CH₂-COOH + Br₂/PBr₃ → R-CHBr-COOH. α-halogenation via acyl bromide enol. Ch 27.

Henry (nitroaldol) — R-CH₂-NO₂ + R'-CHO + base → R-CH(NO₂)-CH(OH)-R'. β-nitroalcohol; reducible to β-aminoalcohol. Ch 30.

Hofmann elimination — R₃N⁺(CH₃)OH⁻ + heat → least-substituted alkene (Hofmann product) + amine. Steric bulk + leaving-group origin. Ch 12, 30.

Hofmann rearrangement — RCONH₂ + Br₂/NaOH → R-NH₂ + CO₂ (one C shorter). Concerted with retention at R. Ch 30.

Horner-Wadsworth-Emmons (HWE) — phosphonate ester ylide (EtO)₂P(=O)-CHR-CO₂R' + base → adds to aldehyde → E-α,β-unsat ester. E-selective; water-soluble byproduct (vs Wittig's Ph₃PO). Ch 25.

Hunsdiecker — RCOOAg + Br₂ → R-Br + CO₂ + AgBr. Radical decarboxylative halogenation. Ch 27.

J

Jacobsen epoxidation — Mn-salen catalyst + NaOCl → asymmetric epoxidation of cis-alkenes (esp. cis-disub and trisub). Complements Sharpless (which needs allylic OH). Ch 36.

Julia olefination — phenyl sulfone + aldehyde → β-hydroxy sulfone → reduction → E-alkene (classical Julia). Modified Julia-Kocienski (BT, PT, TBT sulfones) goes one-pot; E-selective. Ch 25.

K

Kiliani-Fischer synthesis — aldose + HCN → cyanohydrin → reduce/hydrolyze → next-larger aldose. Sugar chain extension. Ch 38.

Knoevenagel condensation — active methylene compound (malonate, β-ketoester) + aldehyde + amine base → α,β-unsat dicarbonyl. Doebner mod (in pyridine) gives decarboxylation to α,β-unsat acid. Ch 28.

Kolbe-Schmitt — phenolate + CO₂/heat/pressure → salicylate. Industrial synth of aspirin precursor. Ch 21.

L

Lemieux-Johnson oxidation — OsO₄ + NaIO₄ → diol intermediate → cleavage → 2 carbonyls. Mild ozonolysis alternative. Ch 36.

Lindlar reduction — alkyne + H₂/Pd-CaCO₃/Pb(OAc)₂(quinoline) → cis-alkene. Selective for syn semi-reduction. Ch 17.

M

Mannich reaction — non-enol carbonyl + HCHO + amine·HCl → β-aminoketone (Mannich base). Iminium electrophile. Ch 29.

Markovnikov's rule (1869) — HX + alkene → H to more H-substituted C (cation stability). Anti-Markov: with peroxides for HBr (radical), or hydroboration. Ch 15.

Matteson homologation — boronic ester + LiCHCl₂ → α-chloroboronate → R-M displaces Cl → homologated stereodefined boronate. Iterative C-C bond construction. Ch 37.

McLafferty rearrangement — mass spectrometric γ-H transfer + β-cleavage → enol cation + alkene. Diagnostic for carbonyls with γ-H. Ch 6.

Meerwein-Ponndorf-Verley (MPV) — ketone + i-PrOH + Al(OiPr)₃ → 2° alcohol + acetone. Reversible hydride transfer; six-membered TS. Reverse = Oppenauer. Ch 36.

Meinwald rearrangement — α,β-epoxyketone → 1,3-dicarbonyl. Lewis acid-catalyzed. Ch 16.

Michael addition — soft nucleophile (stabilized enolate, malonate, amine) + α,β-unsat carbonyl → 1,4-adduct (conjugate addition). Cornerstone of Robinson annulation. Ch 29.

Mitsunobu reaction — R-OH + Nu-H (acidic, pKa < ~13) + PPh₃ + DIAD → R-Nu + Ph₃PO + reduced DIAD. SN2 with inversion at C-OH. Excellent for esters, ethers, azides, phthalimides; sets stereochem. Ch 25.

Mukaiyama aldol — silyl enol ether + aldehyde + Lewis acid (TiCl₄, BF₃·OEt₂) → β-hydroxyketone. Avoids basic conditions; chiral Lewis acids → asymmetric. Ch 28.

N

Nazarov cyclization — divinyl ketone + acid → cyclopentenone. 4π-conrotatory electrocyclization. Ch 39.

Negishi coupling (Nobel 2010) — Pd-cat. R-ZnX + R'-X → R-R'. Tolerates many FGs; sp³-sp² couplings possible. Ch 37.

NBS bromination — N-bromosuccinimide. Allylic/benzylic radical bromination (with light/AIBN); also α-bromination of carbonyls in mild acidic conditions; bromohydrin formation in aq. DMSO. Ch 18.

Noyori asymmetric hydrogenation (Nobel 2001) — Ru-BINAP catalyst + H₂ + β-ketoester → β-hydroxyester with >95% ee. Industrial-scale chiral reduction. Ch 36.

O

Olefin cross metathesis (CM) — Grubbs II/III on two terminal alkenes → cross-product + ethylene. Selectivity by alkene "type" (I: terminal/allyl; II: styrene; III: enone; IV: vinyl heteroatom). Ch 37.

Oppenauer oxidation — 2° alcohol + acetone + Al(OiPr)₃ → ketone + i-PrOH. Reverse of MPV; selective for 2° OH in presence of sensitive groups. Ch 36.

Oxymercuration-demercuration — alkene + Hg(OAc)₂/H₂O → β-hydroxymercurial → NaBH₄ → Markovnikov alcohol. No rearrangement. Ch 16.

Ozonolysis — alkene + O₃ → ozonide → reductive (Me₂S, Zn, PPh₃) → 2 carbonyls; oxidative (H₂O₂) → carboxylic acids. Ch 16.

P

Paal-Knorr synthesis — 1,4-diketone + amine → pyrrole (or H₂S → thiophene, H₂O → furan). Ch 23.

Paterno-Büchi — carbonyl + alkene + hν → oxetane. [2+2] photocycloaddition. Ch 19.

Pauson-Khand — alkyne + alkene + CO + Co₂(CO)₈ → cyclopentenone. [2+2+1] formal cycloaddition. Ch 37.

Petasis reaction — boronic acid + amine + α-hydroxyaldehyde → β-aminoalcohol. Multicomponent; mild. Ch 38.

Peterson olefination — α-silyl carbanion (TMSCH₂Li) + carbonyl → β-hydroxysilane → β-elimination → alkene. Choose acid (anti) or base (syn) elim for E/Z. Ch 25.

Pictet-Spengler — β-arylethylamine + aldehyde → tetrahydroisoquinoline (via iminium + intramolec. EAS). Alkaloid synthesis. Ch 23.

Pinacol rearrangement — 1,2-diol + H⁺ → ketone (with 1,2-migration). Migration aptitude: H > Ar > 3° alkyl > 2° > Me. Ch 16.

Prilezhaev epoxidation — alkene + peracid (mCPBA) → epoxide. Concerted "butterfly" TS; syn. Ch 16.

Prins reaction — alkene + HCHO + H⁺ → 1,3-diol or 1,3-dioxane (depending on conditions). Ch 16.

R

Reformatsky — α-haloester + Zn + carbonyl → β-hydroxyester. Predecessor of modern aldol. Ch 28.

Reimer-Tiemann — phenol + CHCl₃/NaOH → o-hydroxybenzaldehyde. Dichlorocarbene as electrophile in EAS. Ch 21.

Riley oxidation — allylic CH + SeO₂ → α,β-unsat carbonyl (or allylic alcohol with reductive workup). [2,3]-sigmatropic of allylselenenic acid. Ch 36.

Ring-closing metathesis (RCM) — Grubbs cat. on diene → cyclic alkene + ethylene. Best for 5-7 membered rings; macrocyclization with high dilution. Ch 37.

Ritter reaction — 3°-alcohol or alkene + nitrile + H₂SO₄ → N-substituted amide. Cation + nitrile lone pair → nitrilium → H₂O → amide. Ch 30.

Robinson annulation — methyl vinyl ketone (MVK) + cyclic ketone enolate → Michael → intramol aldol/dehydration → 2-cyclohexenone fused ring. Cornerstone of steroid synthesis. Ch 29.

Rubottom oxidation — silyl enol ether + mCPBA → α-hydroxy ketone. Epoxidation then 1,4-Si migration. Ch 36.

S

Sandmeyer — Ar-N₂⁺ + CuCl/CuBr/CuCN → Ar-Cl/Br/CN. Radical mechanism via Cu(I)/Cu(II). Ch 30.

Saponification — ester + NaOH → carboxylate + alcohol. Irreversible (carboxylate is unreactive). Ch 26.

Schiemann reaction — Ar-N₂⁺ BF₄⁻ + heat → Ar-F + N₂ + BF₃. Aryl fluoride synthesis via diazonium tetrafluoroborate. Ch 30.

Shapiro reaction — tosylhydrazone + 2 RLi → vinyllithium (after N₂ loss) → carbonyl/electrophile traps. Carbonyl → vinyl synthon. Ch 25.

Sharpless asymmetric dihydroxylation (AD) — alkene + OsO₄/K₃Fe(CN)₆/(DHQD)₂PHAL (or DHQ) → cis-diol with high ee. AD-mix-α / AD-mix-β. Ch 36.

Sharpless asymmetric epoxidation (Nobel 2001) — allylic alcohol + t-BuOOH/Ti(OiPr)₄/(R,R)- or (S,S)-DET → (2S,3S)- or (2R,3R)-epoxy alcohol. Predictable face (mnemonic: DET enantiomer dictates which face delivers O). Ch 8, 16, 36.

Simmons-Smith cyclopropanation — alkene + CH₂I₂/Zn(Cu) → cyclopropane. Carbenoid; stereospecific syn-addition; OH directs (Furukawa mod). Ch 16.

Skraup synthesis — aniline + glycerol + H₂SO₄/oxidant → quinoline. Acrolein generated in situ. Ch 23.

Sonogashira coupling — Pd/Cu(I) cat. Ar-X + H-C≡C-R → Ar-C≡C-R. Cu-acetylide transmetallation. Ch 17, 37.

Staudinger reaction — R-N₃ + PPh₃ → R-N=PPh₃ (iminophosphorane) → H₂O → R-NH₂ + Ph₃PO. Mild azide reduction; the aza-Wittig variant traps carbonyls. Ch 30.

Stetter reaction — NHC catalyst + aldehyde → acyl anion equivalent → Michael adds to α,β-unsat carbonyl → 1,4-dicarbonyl. Umpolung. Ch 29.

Stille coupling — Pd-cat. Ar-X + R-SnBu₃ → Ar-R. Tolerates many FGs; toxic tin byproducts limit use. Ch 37.

Stork enamine alkylation — ketone + 2° amine → enamine → R-X → iminium → H₃O⁺ → α-alkylated ketone. Mild alternative to enolate alkylation. Ch 29.

Strecker synthesis — RCHO + NH₃/HCN → α-aminonitrile → H₃O⁺ → α-amino acid (racemic). Asymmetric variants with chiral amines or catalysts. Ch 30, 38.

Suzuki-Miyaura coupling (Nobel 2010) — Pd-cat. Ar-X + Ar'-B(OH)₂ + base → Ar-Ar'. Tolerant of water, FGs; the most-used cross-coupling in pharma. Ch 23, 37.

Swern oxidation — DMSO + (COCl)₂, then alcohol, then Et₃N → ketone/aldehyde. Mild, low-temp; byproducts are CO, CO₂, Me₂S (smelly). Ch 36.

T

Tebbe olefination — Cp₂Ti=CH₂ (Tebbe reagent) + carbonyl → methylene alkene. Methylenates esters/amides (which Wittig cannot easily). Ch 25.

U

Ugi reaction — RCHO + R'NH₂ + R''COOH + R'''NC → α-acylaminoamide (4-component, single pot). High structural diversity for combinatorial libraries. Ch 38.

Ullmann coupling — Cu-cat. 2 Ar-X → Ar-Ar. Classical biaryl coupling; modern variants use Cu/ligand at mild temp. Ch 37.

V

Vilsmeier-Haack — DMF + POCl₃ → chloroiminium → EAS on electron-rich arene → hydrolysis → Ar-CHO. Formylation of activated arenes (pyrroles, indoles, phenols). Ch 21.

W

Wacker oxidation — terminal alkene + PdCl₂/CuCl₂/O₂/H₂O → methyl ketone (Markovnikov). Industrial acetaldehyde synthesis. Ch 17, 36.

Walden inversion — SN2 backside attack → inversion of configuration at C. Ch 10.

Weinreb amide — R-C(=O)-N(OMe)Me + R'-MgX or R'-Li → R-C(=O)-R' (ketone, no overaddition). N-methoxy chelate stops at tetrahedral intermediate. Also DIBAL → aldehyde. Ch 25.

Williamson ether synthesis — R-O⁻Na⁺ + R'-X → R-O-R' (SN2; R'-X must be 1° or methyl). Ch 10.

Wittig reaction (Nobel 1979) — Ph₃P=CR₂ + R'R''C=O → alkene + Ph₃PO. Unstabilized ylide (alkyl) → Z; stabilized ylide (ester-, ketone-conjugated) → E. Ch 25.

Wohl-Ziegler bromination — NBS + alkene + (PhCO)₂O₂ or hν → allylic bromide. Same operation as NBS allylic/benzylic. Ch 18.

Wolff-Kishner reduction — R-C(=O)-R' + H₂N-NH₂/KOH/heat (ethylene glycol or DMSO) → R-CH₂-R' + N₂. Strong-base complement to Clemmensen (acid). Ch 21, 36.

Wurtz coupling — 2 R-X + 2 Na → R-R + 2 NaX. Radical coupling; lots of mixed products with two different RX. Mostly of historic interest. Ch 10.

Y

Yamaguchi macrolactonization — seco acid + 2,4,6-trichlorobenzoyl chloride + DMAP → macrolactone. Standard method for natural-product macrolides. Ch 26.

Z

Zaitsev's rule — E1/E2 → most-substituted alkene preferred (when reaction is unbiased; sterically hindered bases reverse to Hofmann). Ch 12.

By transformation cross-index

C-C bond formation — Aldol, Claisen, Diels-Alder, Heck, Suzuki, Negishi, Stille, Sonogashira, Michael, Mannich, Wittig, HWE, Julia, Peterson, Grignard, Reformatsky, Knoevenagel, Henry, Mukaiyama aldol, Evans aldol, Stetter, Stork enamine, Robinson annulation, Pauson-Khand, Glaser, Ullmann, Wurtz, Corey-Chaykovsky, Matteson, Tebbe, Petasis, Ugi.

C-N bond formation — Buchwald-Hartwig, Chan-Lam, Gabriel, Mitsunobu, Fukuyama, reductive amination, Staudinger, Curtius, Hofmann rearrangement, Beckmann, Ritter, Mannich, Strecker, Eschweiler-Clarke.

C-O bond formation — Williamson, Mitsunobu, Fischer esterification, Sharpless AE/AD, Jacobsen, Prilezhaev epoxidation, Baeyer-Villiger, Rubottom, oxymercuration, hydroboration-oxidation, Brown, Wacker, Dakin, Yamaguchi.

Oxidation — Swern, Dess-Martin, Jones, PCC, Wacker, Riley (SeO₂), Lemieux-Johnson, ozonolysis, Baeyer-Villiger, Rubottom, Oppenauer, Sharpless AE/AD, Jacobsen.

Reduction — Clemmensen, Wolff-Kishner, Birch, MPV, Noyori asymmetric, Lindlar, DIBAL, Cannizzaro, Barton-McCombie, Staudinger.

Rearrangements — Beckmann, Curtius, Hofmann, Schmidt, Wolff, Claisen, Cope, Oxy-Cope, Pinacol, Meinwald, Carroll, Favorskii, Bamberger, Nazarov, Bergman.

Cycloadditions — Diels-Alder, [3+2] dipolar, Paterno-Büchi, Pauson-Khand, [2+2] photochemical.

Electrocyclic / sigmatropic — Nazarov, Bergman, Claisen, Cope, [1,3]/[1,5]/[1,7]-H shifts.

Cross-coupling (Pd, Cu, Ni) — Suzuki, Negishi, Stille, Sonogashira, Heck, Buchwald-Hartwig, Chan-Lam, Glaser, Ullmann, Kumada, Hiyama.

Aromatic synthesis — EAS family, Friedel-Crafts (alk/acyl), Kolbe-Schmitt, Reimer-Tiemann, Vilsmeier-Haack, Sandmeyer, Schiemann, Fischer indole, Skraup, Friedländer, Chichibabin, Pictet-Spengler, Paal-Knorr.

Eliminations — E1, E2, E1cb, Hofmann, Cope (oxide), Shapiro, Peterson, Bamford-Stevens, Burgess.

α-Functionalization — HVZ, haloform, Stork enamine, direct enolate alkylation, Mannich, Evans aldol, Rubottom.

Carbonyl → alkene — Wittig, HWE, Julia, Peterson, Tebbe, McMurry.

Carbonyl → CH₂ — Clemmensen, Wolff-Kishner, Mozingo (thioacetal/Raney Ni), Barton-McCombie (after reduction).

Ring-contraction / expansion — Favorskii (contract), Tiffeneau-Demjanov (expand), Beckmann (expand), Baeyer-Villiger (expand by O), pinacol (contract).

~95 named reactions. The core ~40 are required vocabulary; the remainder you'll meet in pharma, total synthesis, and methodology papers.