A Selenourea-Thiourea Brønsted Acid Catalyst Facilitates Asymmetric Conjugate Additions of Amines to α,β-Unsaturated Esters

Overview

Journal J Am Chem Soc

Publisher American Chemical Society

Specialty Chemistry

Date 2020 Mar 3

PMID 32118419

Citations 9

Authors

Yingfu Lin

William J Hirschi

Anuj Kunadia

Anirudra Paul

Ion Ghiviriga

Khalil A Abboud

Rachael W Karugu

Mathew J Vetticatt

Jennifer S Hirschi

Daniel Seidel

Affiliations

Soon will be listed here.

Abstract

β-Amino esters are obtained with high levels of enantioselectivity via the conjugate addition of cyclic amines to unactivated α,β-unsaturated esters. A related strategy enables the kinetic resolution of racemic cyclic 2-arylamines, using benzyl acrylate as the resolving agent. Reactions are facilitated by an unprecedented selenourea-thiourea organocatalyst. As elucidated by DFT calculations and C kinetic isotope effect studies, the rate-limiting and enantiodetermining step of the reaction is the protonation of a zwitterionic intermediate by the catalyst. This represents a rare case in which a thiourea compound functions as an asymmetric Brønsted acid catalyst.

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