Reaction Summary

Nucleophilic substitution: alkyl-leaving group ! alkyl-nucleophile Nucleophile LG Aprotic polar solvent Concerted reaction (SN2) Nu LG Nucleophile Nu Protic solvent Via carbocation intermediate (SN1)

Elimination: alkyl-leaving group ! alkene Strong base LG heat OH H2SO4 heat

Concerted reaction (E2)

Via carbocation intermediate (E1)

Halogen addition: alkene ! vicinal dihaloalkane or halohydrin OH Br2 H2O Br ROH addition: alkene ! alcohol or ether OH H2SO4 H2O H2SO4 R Br2 CH2Cl2 Br Markovnikov addition (no stereochem constraints) Br Anti addition (cyclic bromonium ion)

ROH Via carbocation intermediate Oxymercuration/reduction: alkene ! alcohol or ether OH 1. Hg(OAc) / H O 2 2 2. NaBH4 1. Hg(OAc)2 / ROH 2. NaBH4 R

Markovnikov addition (Anti addition)

Hydroboration/oxidation: alkene ! alcohol 1. BH3 2. NaOH/H2O2 Ozonolysis: alkene ! carboxylic acids or aldehydes OH O O OH H 1. O3 2. H2O2 1. O3 2. (CH3)2S H O O H H OH Anti-Markovnikov addition (Syn addition)

Tosylate synthesis: alcohol ! tosylate Tosyl chloride O (TsCl) Cl S CH3 OH O Pyridine Alkyl halide synthesis: alcohol ! alkyl halide Br PBr3 OH SOCl2 Pyridine Alcohol oxidation: alcohol ! aldehyde OH (PCC) CrO3 Pyridine O H

R-OTs O O S O CH3

Cl

Alcohol oxidation: alcohol ! carboxylic acid or ketone OH K2Cr2O7 O OH Glycol oxidation: glycol ! aldehyde and/or ketone HO OH H5IO6 O O H OH K2Cr2O7 O

Nucleophilic substitution: alkyl-leaving group ! alcohol O NaOH/H2O O CH3 LG Aprotic polar solvent O CH3 Concerted reaction (SN2) O

For secondary substrates OH

Hydrogenation: alkene ! alkane H2 Pd/C Hydrogenation: alkyne ! alkane H2 Pd/C Hydrogenation: alkyne ! alkene trans Na NH3 H2 Lindlar cis

Hydrogenation: aromatic ! aromatic or to alkane H2 Pd/C H2 Pt, high pressure

Glycol synthesis: alkene ! glycol OsO4 H2O/t-butyl alcohol pyridine/TMAO

HO

OH Syn addition

Epoxide synthesis: alkene ! epoxide O m-chloroperoxy- Cl OH benzoic O acid (MCPBA) O Syn addition

Epoxide synthesis: halohydrin ! epoxide Br NaOH (1 equiv) O OH SN2 attack by hydroxyl on carbon with Br

Epoxide ring-opening (basic): epoxide ! alcohol and nucleophile O 1. Nucleophile (basic conditions) 2. Protonate product Nu OH (Example: if the nucleophile is an alcoxide (RO), the result is an alcohol/ether; note that the nucleophile is on the less substituted carbon.)

Epoxide ring-opening (acidic): epoxide ! alcohol and nucleophile O Nucleophile H2SO4 Nu (Example: if the nucleophile is an alcohol, the result is an alcohol/ether); note that the nucleophile is on the more substituted carbon.)

OH

Epoxide ring-opening (Grignard) epoxide ! alcohol two carbons longer O Oxirane 1. R-Mg-Br 2. Protonate product R OH Note: this only yields predictable product when using oxirane)

HX addition: alkyne ! vinyl halide HBr Br Hydration: alkyne ! ketone Hg2+/H2O O Markovnikov addition followed by enol/keto tautomerization Anti-Markovnikov addition (Syn addition) followed by enol/keto tautomerization Note: excess HBr will result in geminal dibromide following second HBr addition

Hydroboration/oxidation: alkyne ! aldehyde 1. BH(amyl)2 2. NaOH/H2O2 H O

Grignard synthesis: alkyne ! Grignard reagent CH3CH2MgBr MgBr ether Grignard synthesis: haloalkane ! Grignard reagent Mg R Br R MgBr ether

EAS Nitration: aromatic ! nitro-aromatic HNO3 H2SO4 EAS Halogenation: aromatic ! halo-aromatic X2 FeX3 (X= Cl, Br, I) Friedel-Crafts Alkylation: aromatic ! alkyl-aromatic R R R + others R H2SO4 Friedel-Crafts Acylation: aromatic ! acyl-aromatic O O R AlCl3 EAS Sulfonation: aromatic ! aromatic sulfonic acid SO3 H2SO4 Benzylic/allylic bromination O CH3 N Br O NBS Br CH2 SO3H Cl R X NO2

R-Cl AlCl3

R + others

Benzylic oxidation: alkyl-aromatic ! aromatic carboxylic acid O R KMnO4 OH

Nucleophilic aromatic substitution: aryl halide ! aryl-nucleophile Note: at least X Nucleophile Nu one activating group in ortho or para position is necessry A A