A Facile Approach to Oximes and Ethers by a Tandem NO+ -Initiated Semipinacol Rearrangement and H-Elimination

Jia-Wei Dong; Tongmei Ding; Shu-Yu Zhang; Zhi-Min Chen; Yong-Qiang Tu

doi:10.1002/anie.201807861

A Facile Approach to Oximes and Ethers by a Tandem NO⁺ -Initiated Semipinacol Rearrangement and H-Elimination

Angew Chem Int Ed Engl. 2018 Oct 1;57(40):13192-13196. doi: 10.1002/anie.201807861. Epub 2018 Sep 6.

Authors

Jia-Wei Dong¹, Tongmei Ding¹, Shu-Yu Zhang¹, Zhi-Min Chen¹, Yong-Qiang Tu^{1

2}

Affiliations

¹ School of Chemistry and Chemical Engineering and, Shanghai Key Laboratory for Molecular Engineering of Chiral Drugs, Shanghai Jiao Tong University, 800 Dongchuan Road, Shanghai, 200240, P. R. China.
² State Key Laboratory of Applied Organic Chemistry and College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou, 730000, P. R. China.

PMID: 30126040
DOI: 10.1002/anie.201807861

Abstract

An efficient oximation method has been developed on the basis of NO⁺ -initiated semipinacol rearrangement and subsequent proton elimination. The procedure enabled the rapid construction of a series of oximes and oxime ethers with spiro quaternary stereocenters from allylic silyl ethers. Additional features of this reaction include wide substrate tolerance as well as the commercial availability of the safe nitrosation reagent NOBF₄ . The key N-heterotricyclic cores of three natural alkaloids, tuberostemoninol B, (+)-quebrachidine, and an insecticide, were also constructed efficiently by this method.

Keywords: oxime ethers; oximes; quaternary centers; semipinacol rearrangement; spiro compounds.

Publication types

Research Support, Non-U.S. Gov't