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