Preparation and Carbocupration–Silylation of Allyl Propiolates: Vicinal Functionalization To Form Polysubstituted (E)-Vinylic Silanes

This work is dedicated to the memory of Dr. Michael P. Jennings, a beloved mentor, friend, and father.

Abstract

The preparation and TMSOTf-mediated catalytic carbocupration–silylation of allylic propiolates has been investigated, expanding on previous syntheses of a variety of β-alkyl- and β-aryl-substituted vinylsilanes from an ethyl propiolate precursor. With few exceptions, the series of synthesized O-allyl (E)-vinylsilanes has been isolated in high yields (61–89%) with exceptional diastereoselectivities (E/Z >20:1). Additionally, we demonstrated a novel LDA-initiated, TMSCl-mediated Ireland–Claisen rearrangement of a representative allylic ester.

Key words

carbocupration - Mitsunobu esterification - Ireland–Claisen rearrangement - allyl esters - Kharasch reagents - vinylsilanes - silyl ketene acetals

Publication History

Received: 21 June 2023

Accepted after revision: 05 October 2023

Accepted Manuscript online:
05 October 2023

Article published online:
15 November 2023

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