Orgo Ch.12 Reactions/Reagents

Alcohol deprotonation (ROH → RO-)

NaH

Alcohol deprotonation with a metal (ROH → RO-)

Li, Na, or K

Alkoxide protonation (RO- → ROH)

H₂SO₄/H₂O or HCl/H₂O

Hydroboration–oxidation ( Alkene → Alcohol)

1) BH₃·THF 2) H₂O₂, NaOH

NaBH₄ reduction (Aldehyde → 1 Alc, Ketone → 2 Alc)

NaBH₄, MeOH

LiAlH₄ (LAH) reduction (Aldehyde → 1° alcohol; Ketone → 2° alcohol; Ester → alcohol(s); Carboxylic acid → 1° alcohol)

1) LiAlH₄ 2) H₃O⁺

Grignard reagent formation ( R–X → R–MgX)

Mg, ether

Grignard reaction: aldehyde/ketone (Aldehyde + RMgX → alcohol with new C–C bond, Ketone + RMgX → 3° alcohol)

1) RMgX 2) H₃O⁺

Grignard reaction: ester (Ester + 2 RMgX → 3° alcohol)

1) excess RMgX 2) H₃O⁺

Anti dihydroxylation (Alkene → anti-1,2-diol)

1) RCO₃H 2) H₃O⁺

Syn dihydroxylation (Alkene → syn-1,2-diol)

1) KMnO₄ 2) NaOH, cold

TMS alcohol protection (ROH → RO–TMS)

TMSCl, NEt₃ (TEA)

TMS alcohol deprotection (RO–TMS → ROH)

TBAF

Alcohol → alkyl bromide (ROH → RBr)

HBr

Alcohol → alkyl chloride (ROH → RCl)

HCl, ZnCl₂

Tosylation (R-OH → ROTS)

TsCl, pyridine

Tosylate SN2 substitution (R–OTs → R–Nu)

Nu⁻

Thionyl chloride substitution (ROH → RCl)

SOCl₂, pyridine

PBr₃ substitution (ROH → RBr)

PBr₃

Acid catalyzed alcohol dehydration (E1) (OH → alkene + h2o)

concentrated H₂SO₄, heat

Tosylate elimination (E2) (OH → alkene)

1) TsCl, pyridine 2) strong base

Chromic acid oxidation (1 degree alc- carboxylic acid, 2 degree- ketone)

H₂CrO₄

Jones type oxidation (1° alcohol → carboxylic acid; 2° alcohol → ketone)

Na₂Cr₂O₇, H₂SO₄, H₂O

PCC oxidation (1° alcohol → aldehyde; 2° alcohol → ketone)

PCC

DMP oxidation (1° alcohol → aldehyde; 2° alcohol → ketone)

DMP (Dess–Martin periodinane), CH₂Cl₂

Swern oxidation (1° alcohol → aldehyde; 2° alcohol → ketone)

1) DMSO, (COCl)₂ 2) NEt₃, low temperature

Phenol oxidation ( Phenol → oxidized quinone-type product)

Na₂Cr₂O₇, H₂SO₄, H₂O