Organic Chemistry

Named Reactions

ChemVidya Definitive Edition · 9 parts · 161 sections · about 126,081 words

Every named reaction the CSIR-NET, GATE and IIT-JAM papers actually ask about, each one carried twice: a slow beginner path that pushes every arrow, and a research-grade advanced path with the stereochemistry, the selectivity and the evidence behind the mechanism.

• 9 parts
• 161 sections
• ~126,081 words
• 9 free extracts — one per part
• CSIR-NET · GATE · IIT-JAM

Part 1 of 9

Foundations & Enolate/Carbonyl Chemistry

The deepest, most rigorous ChemVidya build yet. Two layers on every reaction — a slow, hand-held beginner path and a research-grade advanced/reference path — so one book carries a reader from “I have never pushed an arrow” to “I can propose a mechanism a referee would accept.”

• Bonding, hybridisation and orbitals
• Electronegativity, bond polarity and the dipole map
• Acids, bases and pKa reasoning
• Nucleophiles & electrophiles — the HOMO–LUMO picture
• Curved arrows, taught slowly
• The reactive intermediates — structure & stability
• Resonance vs induction (and the enolate)
• Stereochemistry primer — R/S, E/Z, prochirality
• Thermodynamic vs kinetic control
• The Aldol reaction (addition & condensation)
• Claisen & Dieckmann condensations
• The Mannich reaction
• Michael addition & the Robinson annulation
• Knoevenagel, Perkin & Doebner condensations
• Cannizzaro & Tishchenko reactions
• Benzoin condensation & Stetter reaction (umpolung)
• Darzens glycidic ester condensation
• The Reformatsky reaction
• The Stork enamine synthesis
• The Haloform reaction
• Hell–Volhard–Zelinsky (HVZ) α-halogenation

Read Part 1 — free extract: Bonding, hybridisation and orbitals →

Part 2 of 9

Olefinations & Alkene/Alkyne Construction

How chemists build a C=C (and, at the end, a C≡C) with control over which geometry forms. Two layers on every reaction — a slow, hand-held beginner path and a research-grade advanced/reference path that treats E/Z selectivity, oxaphosphetane and betaine intermediates, stabilised vs non-stabilised ylides, the Schlosser modification and…

• The Wittig olefination
• Horner–Wadsworth–Emmons (HWE) olefination
• Still–Gennari modification (Z-selective HWE)
• Julia & Julia–Kocienski olefination
• Peterson olefination
• Tebbe & Petasis methylenation
• McMurry coupling
• Corey–Fuchs alkyne synthesis
• Seyferth–Gilbert homologation & Ohira–Bestmann modification
• Which olefination do I use? — decision tables

Read Part 2 — free extract: The Wittig olefination →

Part 3 of 9

Organometallic Additions & Carbanion C–C Bond Formation

How chemists use a carbon nucleophile carrying a metal (Mg, Li, Cu, Zn, Cr/Ni) to forge new C–C bonds. Two layers on every reagent — a slow, hand-held beginner path and a research-grade advanced/reference path that treats 1,2- vs 1,4-addition through HSAB, chemoselectivity and protecting-group needs, and addition stereochemistry (Cram /…

• Grignard reagents (RMgX)
• Organolithium reagents (RLi)
• Gilman reagents / organocuprates (R₂CuLi)
• The Corey–House synthesis (alkane from two halides)
• The Barbier reaction (one-pot organometallic addition)
• Organozinc chemistry: the Reformatsky & Blaise reactions
• The Nozaki–Hiyama–Kishi (NHK) reaction
• Reagent → job at a glance
• The 1,2 vs 1,4 rule (HSAB) — the most-tested idea
• Chemoselectivity & reactivity ladder
• Stereochemistry quick-reference

Read Part 3 — free extract: Grignard reagents (RMgX) →

Part 4 of 9

Oxidations & Reductions

How chemists move a molecule up and down the oxidation ladder — adding or removing C–O / C–H bonds under control. Two layers on every reagent: a hand-held beginner path (plain “what it does”, arrow-by-arrow mechanism, graded worked examples, trap boxes) and a research-grade advanced/reference path (stereoelectronics, transition-state and…

• Oxidation-state bookkeeping for carbon (do this first)
• The Swern oxidation (activated DMSO)
• Dess–Martin periodinane (DMP) & IBX (hypervalent iodine)
• Chromium(VI) oxidations: Jones, PCC, PDC, Collins
• The Corey–Kim oxidation
• The Oppenauer oxidation
• Ozonolysis (the Criegee mechanism)
• Epoxidation: peracids (mCPBA / Prilezhaev) and Sharpless AE
• Dihydroxylation: OsO₄ (Upjohn) & Sharpless AD
• The Baeyer–Villiger oxidation (migratory aptitude)
• The Riley oxidation (SeO₂, allylic / α-carbonyl)
• The Étard reaction (chromyl chloride)
• The master ‘which reductant?’ map
• The hydride ladder: LiAlH₄, NaBH₄, DIBAL, L-Selectride, Luche
• Catalytic hydrogenation (incl. Lindlar & Rosenmund)
• Dissolving-metal reductions: Birch & Bouveault–Blanc
• The Wolff–Kishner reduction
• The Clemmensen reduction
• The Meerwein–Ponndorf–Verley (MPV) reduction
• The CBS (Corey–Bakshi–Shibata) reduction
• Noyori / Knowles asymmetric hydrogenation
• Stryker’s reagent ([(Ph₃P)CuH]₆)
• The oxidation ladder — which oxidant, how far?
• ‘Which reductant do I use?’ — master selector
• The three big ‘which-way’ dichotomies
• Asymmetric methods at a glance (Sharpless / CBS / Noyori–Knowles)

Read Part 4 — free extract: Oxidation-state bookkeeping for carbon (do this first) →

Part 5 of 9

Rearrangements

What happens when a molecule reorganises its own skeleton — a group migrates with its bonding electrons from one atom to an adjacent (or, in sigmatropic shifts, a remote) atom, giving a constitutionally different product. Two layers on every reaction: a hand-held beginner path (plain “what it does”, arrow-by-arrow mechanism, graded…

• The 1,2-shift and migratory aptitude (do this first)
• The Pinacol–pinacolone rearrangement
• The Wagner–Meerwein rearrangement
• The Semipinacol rearrangement
• The common thread: acyl nitrene / N–LG, and the isocyanate
• The Beckmann rearrangement
• The Hofmann rearrangement (bromamide degradation)
• The Curtius rearrangement
• The Lossen rearrangement
• The Schmidt reaction
• The Wolff rearrangement & Arndt–Eistert homologation
• The Favorskii rearrangement
• The Benzilic acid rearrangement
• Nomenclature, Woodward–Hoffmann rules, and the chair TS
• The Claisen rearrangement ([3,3], with O)
• The Cope rearrangement ([3,3], all-carbon) & the oxy-Cope
• The Fries rearrangement
• The Stevens [1,2] & Sommelet–Hauser [2,3] rearrangements
• The Dienone–phenol rearrangement
• A four-question triage
• Master comparison tables

Read Part 5 — free extract: The 1,2-shift and migratory aptitude (do this first) →

Part 6 of 9

Aromatic Substitution & Formylation

How new groups are stitched onto a benzene ring — almost the whole Part runs on one machine, electrophilic aromatic substitution (EAS) : an electrophile adds to the aromatic π-system to make a resonance-stabilised arenium (Wheland) ion , then a proton is lost to restore aromaticity . Two layers on every reaction: a hand-held beginner…

• The arenium (Wheland) ion — do this first
• Directing & activating effects — the master logic
• The Friedel–Crafts alkylation
• The Friedel–Crafts acylation
• The Gattermann & Gattermann–Koch formylations
• The Vilsmeier–Haack formylation
• The Reimer–Tiemann reaction
• The Kolbe–Schmitt reaction (phenol carboxylation)
• The Houben–Hoesch reaction (ketone synthesis)
• Diazotisation — making the diazonium salt
• The Sandmeyer reaction (and related diazonium substitutions)
• The Balz–Schiemann reaction (aryl fluorides)
• The Bucherer reaction (naphthol ↔ naphthylamine)
• Azo coupling & the Japp–Klingemann reaction
• SNAr — the addition–elimination mechanism
• The benzyne (elimination–addition) mechanism
• Directing-effects master table
• Aromatic-functionalisation decision guide

Read Part 6 — free extract: The arenium (Wheland) ion — do this first →

Part 7 of 9

Pericyclic Reactions & the Woodward–Hoffmann Rules

The reactions with no intermediate : bonds break and form together, in one concerted step , as electrons flow round a closed loop of overlapping orbitals. Because there is no cation, anion or radical to stabilise, what decides whether a pericyclic reaction happens — and with what stereochemistry — is orbital symmetry , codified by the…

• Three tools that all give the same answer
• The Diels–Alder reaction (the [4+2] cycloaddition)
• Diels–Alder variants: hetero-DA, retro-DA and the Danishefsky diene
• 1,3-Dipolar (Huisgen) cycloaddition — and ‘click’ chemistry
• The [2+2] cycloaddition (photochemical) and Paterno–Büchi
• Cheletropic reactions (both bonds to one atom)
• The con/dis rules — count electrons, check heat or light
• [1,5]- and [1,7]-hydrogen shifts
• The Alder-ene reaction
• Woodward–Hoffmann master selection-rules table
• The general rule and how to apply it
• Quick ‘heat or light?’ lookup
• Mixed research-level problems

Read Part 7 — free extract: Three tools that all give the same answer →

Part 8 of 9

Cross-Couplings & C–C / C–X Bond Formation

The reactions that join two carbon fragments under a metal . A low-valent palladium(0) (or copper) centre acts as a molecular matchmaker: it inserts into a carbon–halide bond ( oxidative addition ), picks up the second carbon from a main-group organometallic ( transmetalation ), and expels the new C–C bond ( reductive elimination )…

• The four elementary organometallic steps
• The Suzuki–Miyaura coupling (organoboron)
• The Negishi coupling (organozinc)
• The Stille coupling (organotin)
• The Kumada–Tamao–Corriu coupling (Grignard)
• The Hiyama coupling (organosilicon)
• The Sonogashira coupling (terminal alkyne + halide)
• The Mizoroki–Heck reaction (alkene arylation)
• The Buchwald–Hartwig amination (C–N coupling)
• The Wacker–Tsuji oxidation (alkene → methyl ketone)
• The Tsuji–Trost allylic alkylation (π-allyl Pd)
• The Chan–Lam coupling (Cu; boronic acid + amine/phenol)
• The Wurtz & Wurtz–Fittig couplings (Na; the classical alkane/arene couplings)
• The Ullmann coupling & condensation (Cu; biaryls and C–heteroatom bonds)
• The Glaser / Eglinton / Hay alkyne couplings (Cu; oxidative diyne formation)
• The Fukuyama coupling (thioester + organozinc → ketone)
• Decision table by organometallic partner (the transmetalation couplings)
• Decision table by target bond / product
• Selectivity & functional-group comparison

Read Part 8 — free extract: The four elementary organometallic steps →

Part 9 of 9

Functional-Group Interconversions, Heterocycle Syntheses & Multicomponent Reactions

The final part gathers the reactions that swap one functional group for another , that build rings containing nitrogen, oxygen and sulfur , and that assemble a complex product from three or four simple pieces in one pot . Three families in one file. Functional-group interconversions: make ethers ( Williamson ), primary amines cleanly (…

• The Williamson ether synthesis
• The Gabriel synthesis (& the Delépine variant)
• The Hofmann elimination (& Hofmann vs Zaitsev)
• The Finkelstein reaction (halide exchange)
• The Appel reaction (alcohol → halide)
• The Hunsdiecker reaction (RCOOAg → R–Br)
• The Mitsunobu reaction (alcohol + acidic Nu, inversion)
• The Ritter reaction (nitrile + carbocation → amide)
• Reductive amination: Eschweiler–Clarke & Leuckart–Wallach
• The Fischer esterification (acid + alcohol ⇌ ester)
• The Strecker amino-acid synthesis
• The Fischer indole synthesis
• The Paal–Knorr synthesis (furan / pyrrole / thiophene)
• The Knorr pyrrole synthesis
• The Hantzsch dihydropyridine / pyridine synthesis
• The Skraup & Doebner–Miller quinoline syntheses
• Bischler–Napieralski & Pictet–Spengler (isoquinolines)
• The Biginelli dihydropyrimidinone synthesis
• The Passerini reaction (3-component)
• The Ugi reaction (4-component)
• The nine parts at a glance
• What Part 9 (this file) contains

Read Part 9 — free extract: The Williamson ether synthesis →

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