Photochemical Strain-Release-Driven Cyclobutylation of C(sp3 )-Centered Radicals

Angew Chem Int Ed Engl. 2020 Feb 10;59(7):2618-2622. doi: 10.1002/anie.201908951. Epub 2019 Nov 6.

Abstract

A new photoredox-catalyzed decarboxylative radical addition approach to functionalized cyclobutanes is described. The reaction involves an unprecedented formal Giese-type addition of C(sp3 )-centered radicals to highly strained bicyclo[1.1.0]butanes. The mild photoredox conditions, which make use of a readily available and bench stable phenyl sulfonyl bicyclo[1.1.0]butane, proved to be amenable to a diverse range of α-amino and α-oxy carboxylic acids, providing a concise route to 1,3-disubstituted cyclobutanes. Furthermore, kinetic studies and DFT calculations unveiled mechanistic details on bicyclo[1.1.0]butane reactivity relative to the corresponding olefin system.

Keywords: bicyclo[1.1.0]butanes; cyclobutanes; late-stage functionalization; photocatalysis; strained molecules.