Asymmetric Allylic Alkylation of Acyclic Allylic Ethers with Organolithium Reagents

Abstract

A highly efficient, regio- and enantioselective Cu(I)/phosphoramidite-catalyzed asymmetric allylic alkylation of allyl ethers with organolithium reagents is reported (see scheme). The use of organolithium reagents is essential for this catalytic C-C bond formation due to their compatibility with different Lewis acids. The versatility of allylic ethers under the copper-catalyzed reaction conditions with organolithium reagents is demonstrated in the shortest synthesis of (S)-Arundic acid.

Enantioselective and Enantiospecific Transition-Metal-Catalyzed Cross-Coupling Reactions of Organometallic Reagents To Construct C–C Bonds

“… 308 A recent study has shown that addition of a Lewis acid can enable the use of methyl or benzyl ethers as leaving groups, increasing the scope of the electrophile. 309 …”

Transition metal-catalyzed allylic substitution reactions with unactivated allylic substrates

“…81 Allylic ethers bearing OMe and OBn groups provided the best results and regioselectivity was improved via the in situ generation of BF 2 OTf from BF 3 ÁOEt 2 and TMSOTf (Table 20). 81 Allylic ethers bearing OMe and OBn groups provided the best results and regioselectivity was improved via the in situ generation of BF 2 OTf from BF 3 ÁOEt 2 and TMSOTf (Table 20).…”

Transition-metal-free allylation of 2-azaallyls with allyl ethers through polar and radical mechanisms

“…2b) and isochromene derivatives via SET from the 2-azaallyl anion, radical cyclization, and finally intermolecular radical-radical coupling reactions 97,98 . Based on the unusual reactivity of 2-azaallyl anions, we were curious about their ability to react with allyl electrophiles that bear leaving groups that were generally categorized as poor in both organic chemistry and in the presence of transition-metal allylation catalysts [99][100][101][102][103] .…”