Isami Hamamoto

Denitrohydrogenation of aliphatic nitro compounds and a new use of aliphatic nitro compounds as radical precursors

Abstract Aliphatic nitro groups are replaced by hydrogen on treatment with tributyltin hydride which proceeds via free radical chain processes. As the nitro group is selectively denitrated and other reducible groups are not affected with tributyltin hydride, this reaction can be used as a method for removing the nitro group from polyfunctional compounds. The radical intermediates generated via denitration can be also used for the carbon-carbon bond forming reactions.

A new olefin synthesis. Synchronous elimination of nitro and ester groups or nitro and keto groups from .beta.-nitro esters or .beta.-nitro ketones

Synthese de nitriles, esters, cetones et sulfones vinyliques a partir de (chloro-1 nitro-1) ou de (bromo-1 nitro-1) alcanes

Regio-and stero-selective γ-substitution of allylic nitro compounds with lithium dialkylcuprates

Regio-and stereo-selective γ-Substitution of allylic nitro compounds with lithium dialkylcuprates provides a new synthesis for trisubstituted olefins.

Palladium-catalysed allylic alkylations of allylic nitro-compounds

In the presence of catalytic amounts of tetrakis(triphenylphosphine)palladium, allylic nitro-compounds undergo allylic alkylations with sodium dimethyl malonate.

Palladium-catalysed allylic alkylation of allylic nitro compounds with stabilized carbanions

In the presence of a catalytic amount of Pd(PPh3)4, allylic nitro compounds (1) undergo allylic alkylation with stabilized carbanions to give a mixture of two regio-isomers (2) and (3). The product ratio (2) : (3) is controlled both by the nature of the substituents of π-allyl unit and the steric factors of the nucleophiles and ligands.

Direct conversion of allylic nitro compounds into allyl sulphides and allyl sulphones

Allylic nitro compounds are directly converted into allyl sulphides or allyl sulphones with high regioselectivity on treatment with sodium benzenethiolate alone or with sodium benzenesulphinate in the presence of a catalytic amount of Pd(PPh3)4.