Reduction Reagents

Reducing Reagents
Reagent Sodium Borohydride NaBH4 Preferred Solvents ethanol; aqueous ethanol 15% NaOH; diglyme avoid strong acids Functions Reduced aldehydes to 1-alcohols ketones to 2-alcohols 1,2-reduction of enones is favored by CeCl3 inert to most other functions aldehydes to 1-alcohols ketones to 2-alcohols carboxylic acids to 1-alcohols esters to alcohols epoxides to alcohols nitriles & amides to amines halides & tosylates to alkanes most functions react fast: acid chlorides to aldehydes (at -78 C) 3-amides to aldehydes (at -78 C) nitriles to aldehydes (at -78 C) slower: aldehydes to 1-alcohols ketones to 2-alcohols fast: acid chlorides to aldehydes (at -78 C) 3-amides to aldehydes (at -78 C) nitriles to aldehydes (at -78 C) slower: aldehydes to 1-alcohols ketones to 2-alcohols carboxylic acids to 1-alcohols aldehydes to 1-alcohols ketones to 2-alcohols nitriles to amines esters & epoxides slowly reduced alkenes & alkynes to alkanes Reaction Work-up 1) simple neutralizat ion 2) extracti on of product 1) careful addition of water 2) dissolve aluminum salts 3) extracti on of product 1) careful addition of water 2) dissolve aluminum salts 3) extracti on of product 1) careful addition of water 2) dissolve aluminum salts 3) extracti on of product 1) dilute acid or H2O2 2) extracti on of product filter to

Lithium Aluminum Hydride (LAH) LiAlH4

ether; THF avoid alcohols and amines avoid halogenated compounds avoid strong acids

Lithium tri tButoxyaluminohydride LiAlH(Ot-C4H9)3

ether; THF avoid alcohols and amines avoid halogenated compounds avoid strong acids

Diisobutylaluminum Hydride AlH[CH2CH(CH3)2]2

THF; toluene avoid alcohols and amines avoid halogenated compounds avoid strong acids

Diborane B2H6 = 2 BH3

ether; THF sulfide complex in CH2Cl2 complexes with amines avoid alkenes & alkynes alcohols, ethers,

Hydrogen & Catalyst

H2 & Pt, or Pd, or Ru, or Ni

hydrocarbons or carboxylic acids

Modified (poisoned) Catalyst

(fast) nitro groups to amines (fast) imines to amines (fast) aldehydes & ketones to alcohols (slow) nitriles to amines (slow) may remove benzylic groups alkynes to alkenes acyl chlorides to aldehydes

remove catalyst

Reactive Metals Na, or Li, or K Mg or Al or Zn or Fe

liq. ammonia & ether co-solvents or alcohols or amines

ketones to 2-alcohols alkynes to alkenes conjugated -systems (e.g. aromatic rings, dienes & enones) water, alcohols, acetic cleaves C-X and benzylic groups acid or aqueous mineral cleaves activated substituents acid nitro groups to amines C=O (aldehyde/ketone) to CH2

1) quench with NH4Cl 2) extract product extract product from salts

Many related hydride reagents, having different reductive power and selectivity, incorporate a variety of organic ligands on the hydride carrier atom. Among these are: lithium triethylborohydride (super hydride), potassium tri- sec-butylborohydride (K-Selectride), sodium bis(2-methoxyethoxy)aluminumhydride (Red-Al), sodium cyanoborohydride, sodium triacetoxyborohydride. various organosilanes and in situ generated aluminum hydride and dichlorohydride. Organoborane derivatives having modified reactivity relative to borane itself include: bis(1,2dimethylpropyl)borane (disiamylborane), 9-borabicyclo[3.3.1]nonane (9-BBN) & catecholborane (BHcat).

Oxidation Reagents
Reagent Jones Reagent H2CrO4 Preferred Solvents aqueous sulfuric acid & acetone (avoid acid sensitive systems) Functions Oxidized 1-alcohols to carboxylic acids aldehydes to carboxylic acids 2-alcohols to ketones avoid amines and sufides 1-alcohols to aldehydes 2-alcohols to ketones Reaction Work-up 1) destroy excess reagent 2) extract product 1) filter inorganic salts 2) wash with aqueous acid 3) remove CH2Cl2 sol vent 1) filter

Collins Reagent CrO3 2 C5H5N

methylene chloride (CH2Cl2)

Pyridinium

methylene chloride

1-alcohols to aldehydes

Chlorochromate ClCrO3 C5H5NH

(CH2Cl2)

2-alcohols to ketones

inorganic salts 2) wash with aqueous acid 3) remove CH2Cl2 sol vent 1) neutrali ze reactants 2) remove solvents 1) destroy excess reagent 2) extract product

Dimethyl Sulfoxide (CH3)2S=O & DCC or Ac2O or (CF3CO)2O or SO3 or (COCl)2 Potassium Permanganate KMnO4

CH2Cl2 or ethers or DMSO

A Mild Procedure 1-alcohols to aldehydes 2-alcohols to ketones

water and aqueous solvent mixtures pyridine often used catalytically

Osmium Tetroxide OsO4

aldehydes to carboxylic acids 2-alcohols to ketones alkenes to vicinal-diols (vic.-glycols) alkynes to carboxylic acids avoid amines and sufides alkenes to vicinal-diols (vic.-glycols) vic.-glycols to carbonyl compounds vic.-glycols to carbonyl compounds alkenes to epoxides ketones to esters avoid amines and sufides

Periodic Acid HIO4 Lead Tetraacetate Pb(OCOCH3)4 Peracids CH3CO3H C6H5CO3H, etc.

water or aqueous mixtures benzene or acetic acid CH2Cl2 or ethers

1) destroy excess reagent 2) extract product 1) destroy excess reagent 2) extract product

Ozone O3

CH2Cl2 or CHCl3 (sometimes alcohol)

cleaves alkenes & alkynes 1) destroy avoid benzene derivatives excess amines and sufides reagent & ozonides 2) extract product