Catalytic Asymmetric C-H Insertion Reactions of Vinyl Carbocations

Overview

Journal Science

Specialty Science

Date 2022 Dec 8

PMID 36480623

Authors

Sepand K Nistanaki

Chloe G Williams

Benjamin Wigman

Jonathan J Wong

Brittany C Haas

Stasik Popov

Jacob Werth

Matthew S Sigman

K N Houk

Hosea M Nelson

Affiliations

Soon will be listed here.

Abstract

From the preparation of pharmaceuticals to enzymatic construction of natural products, carbocations are central to molecular synthesis. Although these reactive intermediates are engaged in stereoselective processes in nature, exerting enantiocontrol over carbocations with synthetic catalysts remains challenging. Many resonance-stabilized tricoordinated carbocations, such as iminium and oxocarbenium ions, have been applied in catalytic enantioselective reactions. However, their dicoordinated counterparts (aryl and vinyl carbocations) have not, despite their emerging utility in chemical synthesis. We report the discovery of a highly enantioselective vinyl carbocation carbon-hydrogen (C-H) insertion reaction enabled by imidodiphosphorimidate organocatalysts. Active site confinement featured in this catalyst class not only enables effective enantiocontrol but also expands the scope of vinyl cation C-H insertion chemistry, which broadens the utility of this transition metal-free C(sp)-H functionalization platform.

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