Highly Stereospecific Cyclizations of Homoallylic Silanols

Overview

Journal J Org Chem

Publisher American Chemical Society

Specialty Chemistry

Date 2022 Jul 28

PMID 35901375

Authors

Anand H Shinde

Ranjeet A Dhokale

Joel T Mague

Shyam Sathyamoorthi

Affiliations

Soon will be listed here.

Abstract

We demonstrate that di--butylsilanols are competent nucleophiles for the intramolecular interception of palladium π-allyl species. In these reactions, allyl ethyl carbonates are the best precursors for the formation of palladium π-allyl intermediates, and [(Cinnamyl)PdCl]/BINAP is superior to other Pd salt/ligand framework combinations. Our optimized protocol is compatible with a variety of silanol substrates. Importantly, the cyclization is perfectly stereospecific, proceeding via an - mechanism, which stands in contrast to reported analogous reactions of alcohols and phenols, known to proceed via an - mechanism. The alkenes in the product dioxasilinanes serve as blank slates for further functionalization.

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