Cyclic Oxime Esters as Deconstructive Bifunctional Reagents for Cyanoalkylesterification of 1,6-Enynes

Shi-Chao Wang, Yi-Ting Shen, Tian-Shu Zhang,* Wen-Juan Hao,* Shu-Jiang Tu, Bo Jiang*

A concise copper catalysis strategy for the addition-cyclization of cyclic oxime esters across 1,6-enynes with high stereoselectivity to generate 1-indanones bearing an all-carbon quaternary center is reported. In this process, single-electron reduction of cyclic oxime esters enables deconstructive carbon-carbon cleavage to provide a key cyanopropyl radical poised for the addition-cyclization. This reaction is redox-neutral, exhibits good functional group compatibility, and features 100% atomic utilization. This process driven by copper catalyst makes readily available cyclic oxime esters as bifunctional reagents to demonstrate convergent synthesis.

J. Org. Chem. 2021, 86, 15488-15497; DOI: 10.1021/acs.joc.1c01972