Radical-Mediated Strategies for the Functionalization of Alkenes with Diazo Compounds

Journal of the American Chemical Society
Yong-Liang SuMichael P Doyle

Abstract

One of the most common reactions of diazo compounds with alkenes is cyclopropanation, which occurs through metal carbene or free carbene intermediates. Alternative functionalization of alkenes with diazo compounds is limited, and a methodology for the addition of the elements of Z-CHR2 (with Z = H or heteroatom, and CHR2 originates from N2═CR2) across a carbon-carbon double bond has not been reported. Here we report a novel reaction of diazo compounds utilizing a radical-mediated addition strategy to achieve difunctionalization of diverse alkenes. Diazo compounds are transformed to carbon radicals with a photocatalyst or an iron catalyst through PCET processes. The carbon radical selectively adds to diverse alkenes, delivering new carbon radical species, and then forms products through hydroalkylation by thiol-assisted hydrogen atom transfer (HAT), or forms azidoalkylation products through an iron catalytic cycle. These two processes are highly complementary, proceed under mild reaction conditions, and show high functional group tolerance. Furthermore, both transformations are successfully performed on a gram-scale, and diverse γ-amino esters, γ-amino alcohols, and complex spirolactams are easily prepared with commercially avai...Continue Reading

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Citations

Jun 25, 2021·Chemical Science·Pu ChenMichal Szostak
Jul 17, 2021·Journal of the American Chemical Society·Guangyue LeiJuntao Ye
Jul 24, 2021·Journal of the American Chemical Society·Wen LiuXiaoming Feng
Nov 17, 2021·Organic Letters·Krzysztof R DworakowskiDorota Gryko

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