Reduction of secondary amides to imines and secondary amines has been achieved using low catalyst loadings of readily available iridium catalysts such as [Ir(COE) 2 Cl] 2 with diethylsilane as reductant. Amide reduction is a reaction in organic synthesis where an amide is reduced to either an amine or an aldehyde functional group. [1] reaction mechanism (see Scheme 2 and the SI): (1) The reduction of trans-cyclopropane radical clocks 818 using limiting SmI 2 resulted in rapid cyclopropyl ring opening to give acyclic amides 9and alcohols 10inthefollowing ratios: 78:22 (primary amide), 85:15 (secondary amide), and 92:8 (tertiary amide). Note that this reaction is different to that of other C=Ocompounds which reduce to alcohols; The nature of the amine obtained depends on … The reaction goes by a nucleophilic addition-elimination mechanism and alkoxy groups (RO –), being poor leaving groups, make this method not as practical as, for example, the reaction of acyl chlorides with amines. Amides can be converted to 1°, 2° or 3° amines using LiAlH4. The Mechanism of Amide Reduction by LiAlH 4. The leaving group in ester reduction is the RO – alkoxy group while for amides, the carbonyl oxygen is converted into a leaving group and then eliminated. Lithium Aluminum Hydride ( LiAlH4) is often the reagent of choice for reducing amides to amines. The stepwise reduction to secondary amine proceeds through an imine intermediate that can be isolated when only 2 equiv of silane is used. One drawback is its lack of selectivity. Amides can be reduced by LiAlH 4 but NOT the less reactive NaBH 4; Typical reagents : LiAlH 4 / ether solvent followedby aqueous work-up. General Reaction; Mechanism; Contributors; Since relatively few methods exist for the reduction of carboxylic acid derivatives to aldehydes, it would be useful to modify the reactivity and solubility of LAH to permit partial reductions of this kind to be achieved. Esters can be converted into primary, secondary and tertiary amides by an aminolysis reaction with ammonia, primary amine and a secondary amine respectively:. Primary and secondary amides have a proton connected to the nitrogen that is acidic enough to be attacked by the hydride. This step occurs before the nucleophilic addition of the hydride ion: Example 1: Amide Reductions; Alkyl groups attached to the nitrogen do not affect the reaction. The most fruitful approach to this end has been to attach … Possible Mechanism; Amides can be converted to 1°, 2° or 3° amines using LiAlH4.