Stereoselective Synthesis of 3,4-Dihydrobenzofuro[3,2-b]pyridin-2(1H)-ones Enabled by Pd/Chiral Isothiourea Relay Catalysis

Abstract

A highly enantioselective [4+2] cyclization of azadienes with ketene in situ generated from Pd-catalyzed carbonylation of benzyl bromides, is established through Pd/chiral isothiourea relay catalysis. The key in this transformation is the formation of a C1-ammonium enolate from the in situ generated ketene and a chiral isothiourea catalyst, which subsequently undergoes a formal [4+2] reaction, leading to 3,4-dihydrobenzofuro[3,2-b]pyridine derivatives in high yields and excellent levels of stereoselectivity.

Key words

relay catalysis - C1-ammonium enolate - chiral isothiourea - azadiene - asymmetric catalysis

Publication History

Received: 27 November 2023

Accepted after revision: 22 January 2024

Article published online:
13 February 2024

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