Efficient One-Pot Multifunctionalization of Alkynes en Route to α-Alkoxyketones, α-Thioketones, and α-Thio Thioketals by using an Umpolung Strategy

Zhou Xu; Rongliang Zhai; Ting Liang; Liming Zhang

doi:10.1002/chem.201703087

Efficient One-Pot Multifunctionalization of Alkynes en Route to α-Alkoxyketones, α-Thioketones, and α-Thio Thioketals by using an Umpolung Strategy

Chemistry. 2017 Oct 12;23(57):14133-14137. doi: 10.1002/chem.201703087. Epub 2017 Aug 16.

Authors

Zhou Xu¹, Rongliang Zhai¹, Ting Liang¹, Liming Zhang²

Affiliations

¹ Jiangsu Key Laboratory of New Drug Research and Clinical Pharmacy, Xuzhou Medical University, Tongshan Road 209, Xuzhou, 221004, P.R. China.
² Department of Chemistry & Biochemistry, University of California, Santa Barbara, California, 93106, USA.

PMID: 28683191
DOI: 10.1002/chem.201703087

Abstract

The use of polarized synthons is a highly desirable strategy, as it generally enables unprecedented retrosynthetic disconnections for the synthesis of unique substances. Herein, a new approach for α-oxygenated ketones, α-thioketones and α-thio thioketals via an intermolecular umpolung reaction between nucleophiles (alcohols/thioalcohols) and N-alkenoxypyridinium salts, which were generated from the corresponding alkynes, has been developed for the first time. The reactions proceed with good substrate scope and excellent functional group tolerance in one-pot manner. Applications of the products, α-oxygenated ketones, to the synthesis of other valuable synthetic moieties has also been successfully achieved.

Keywords: alkynes; sulfur; thioketals; thioketones; umpolung.