Work

Construction of Vicinal Quaternary Centers via Ru-Catalyzed Enantiospecific Allylic Substitution with Lithium Ester Enolates

Year: 2024

Type: article

Abstract: High Resolution Image Download MS PowerPoint Slide The installation of vicinal quaternary centers with absolute stereocontrol constitutes a considerable challenge in organic synthesis. Herein, we introduce a novel [Cp*Ru(MeCN) 3 ]PF 6 /phenoxythiazoline catalyst system that achieves enantiospecific allylic substitution of tertiary carbonates with α,α-disubstituted lithium ester enolates to give products containing vicinal quaternary centers. Noteworthy features include the direct use of nonstabilized ester enolates, a class of nucleophiles which has rarely been used in transition metal-catalyzed allylic substitution reactions. The approach is demonstrated for a broad scope of tertiary electrophiles as well as ester enolates and accomplishes stereoretentive substitution with excellent conservation of ee (89–99%) and branched/linear regioselectivities (up to 40:1).

Source: Journal of the American Chemical Society

DOI: 10.1021/jacs.4c07690

Authors: Sven M. Papidocha, Erick M. Carreira

Institutions: ETH Zurich, Laboratory of Organic Chemistry

Language: English

Topic: Asymmetric Synthesis and Catalysis

Subfield: Organic Chemistry

Field: Chemistry

Domain: Physical Sciences

Open Access status: hybrid

Estimated APC paid: $4,500

Funder: Eidgenössische Technische Hochschule Zürich