Preparation of Vinylic Lithium Reagents from Silyl Enolates of Alkyl Aryl Ketones Using Lithium Arenide

Abstract The preparation of vinylic lithium reagents from vinylic halides is a common practice in organic synthesis. However, the preparation of vinylic halides is not always straightforward. In this study, we propose the use of silyl enolates of alkyl aryl ketones as a readily available and efficient alternative for generating vinylic lithium species. Treatment of triisopropylsilyl enolates of alkyl aryl ketones with lithium naphthalenide or lithium 4,4’‐di‐ t ‐butylbiphenylide affords the corresponding vinylic lithium species. This preparation represents a reductive transformation of electron‐rich silyl enolates, which had remained unexplored. This process provides an alternative to the Shapiro reaction and has great potential for various applications in organic synthesis.