Lewis Base Catalyzed Synthesis of Sulfur Heterocycles Via the C1-Pyridinium Enolate

Overview

Journal Angew Chem Int Ed Engl

Specialty Chemistry

Date 2022 Jun 19

PMID 35718884

Authors

Simon Cromwell

Randy Sutio

Changhe Zhang

Georgina K Such

David W Lupton

Affiliations

Soon will be listed here.

Abstract

While the addition of C1-Lewis base enolates to carbonyls and related structures are well established, the related addition to thiocarbonyls compounds are unknown. Herein, we report a reaction cascade in which a C1-pyridinium enolate undergos addition to dithioesters, trithiocarbonates and xanthates. The reaction provides access to a range of dihydrothiophenes and dihydrothiopyrans (28-examples). Mechanistic investigations, including isolation of intermediates, electronic correlation, and kinetic isotope effect studies support the viability of an activated acid intermediate giving rise to the C1-pyridinium enolate which undergoes turnover limiting cyclization. Subsequent formation of a β-thiolactone regenerates the catalyst with loss of carbon oxysulfide providing the observed products.

Citing Articles

Lewis Base Catalyzed Synthesis of Sulfur Heterocycles via the C1-Pyridinium Enolate.

Cromwell S, Sutio R, Zhang C, Such G, Lupton D Angew Chem Int Ed Engl. 2022; 61(33):e202206647.

PMID: 35718884 PMC: 9545057. DOI: 10.1002/anie.202206647.

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