Copper(l) promoted allylic nucleophilic substitutions: a synthetic and mechanistic study

Baruah, Jubaraj B and Samuelson, Ashoka G (1994) Copper(l) promoted allylic nucleophilic substitutions: a synthetic and mechanistic study. In: New Journal of Chemistry, 18 (8-9). pp. 961-971.

PDF Copper.pdf Restricted to Registered users only Download (5MB) | Request a copy

Abstract

Allylic alkylations and substitutions promoted by copper(l) have been studied. These reactions are very useful from the synthetic point of view, since a wide variety of allylic substrates such as halides, esters, carbonates and even alcohols are activated towards substitutions. They can be carried out under acidic conditions and hence complement the widely used palladium catalysed reaction. The driving force for the reaction is the exchange of the poorly coordinating anion on the copper, usually perchlorate or tetrafluoroborate, for a good ligating anion from the allylic substrate. The reaction proceeds through a highly reactive, symmetrical intermediate. The various possibilities include an $\eta^3-\pi$ allylic complex of copper, a fluxional $\eta^2$ complex of the allylic cation and a free cation. Experiments designed to distinguish between the possibilities are described.

Item Type:	Journal Article
Publication:	New Journal of Chemistry
Additional Information:	Copyright of this article belongs to CNRS-Gauthier-Villars.
Department/Centre:	Division of Chemical Sciences > Inorganic & Physical Chemistry
Date Deposited:	18 Aug 2006
Last Modified:	19 Sep 2010 04:31
URI:	http://eprints.iisc.ac.in/id/eprint/8333

Actions (login required)

View Item