Silver-Catalyzed Regio- and Stereoselective Formal Carbene Insertion into Unstrained C-C σ-Bonds of 1,3-Dicarbonyls

Zhaohong Liu; Xinyu Zhang; Matteo Virelli; Giuseppe Zanoni; Edward A Anderson; Xihe Bi

doi:10.1016/j.isci.2018.09.006

Silver-Catalyzed Regio- and Stereoselective Formal Carbene Insertion into Unstrained C-C σ-Bonds of 1,3-Dicarbonyls

iScience. 2018 Oct 26:8:54-60. doi: 10.1016/j.isci.2018.09.006. Epub 2018 Sep 18.

Authors

Zhaohong Liu¹, Xinyu Zhang¹, Matteo Virelli², Giuseppe Zanoni², Edward A Anderson³, Xihe Bi⁴

Affiliations

¹ Department of Chemistry, Northeast Normal University, Changchun 130024, China.
² Department of Chemistry, University of Pavia, Viale Taramelli 12, Pavia 27100, Italy.
³ Chemistry Research Laboratory, University of Oxford, 12 Mansfield Road, Oxford OX1 3TA, UK.
⁴ Department of Chemistry, Northeast Normal University, Changchun 130024, China; State Key Laboratory of Elemento-Organic Chemistry, Nankai University, Tianjin 300071, China. Electronic address: bixh507@nenu.edu.cn.

Abstract

A regio- and stereoselective silver-catalyzed formal carbene insertion into 1,3-dicarbonyls has been developed, using N-nosylhydrazones as diazo surrogates. Two new C-C bonds are constructed at the carbenic carbon center through the selective cleavage of the C-C(=O) σ-bond of acyclic 1,3-dicarbonyls, enabling the preparation of various synthetically useful polysubstituted γ-diketones, γ-ketoesters, and γ-ketoamides in high yields. The in situ formation of a donor-acceptor cyclopropane, via reaction of the enolate of the 1,3-dicarbonyl with an electrophilic silver carbenoid, is proposed as a key process in the catalytic cycle.

Keywords: Catalysis; Chemistry; Organic Synthesis.