Ketones and aldehydes as alkyl radical equivalents for C─H functionalization of heteroarenes.

Abstract:

:The polar nature of the C═O bond commonly allows it to undergo direct attack by nucleophiles at the electrophilic carbon atom in which ketones and aldehydes act as alkyl carbocation equivalents. In contrast, transformations in which ketones and aldehydes act as alkyl radical equivalents (generated in carbonyl carbon) are unknown. Here, we describe a new catalytic activation mode that combines proton-coupled electron transfer (PCET) with spin-center shift (SCS) and enables C─H alkylation of heteroarenes using ketones and aldehydes as alkyl radical equivalents. This transformation proceeded via reductive PCET activation of the ketones and aldehydes to form α-oxy radicals, addition of the radicals to the N-heteroarenes to form C─C bonds, and SCS to cleave the C─O bonds of the resulting alcohols. This mild protocol represents a general use of abundant, commercially available, ketones and aldehydes as latent alkyl radical equivalents.

journal_name

Sci Adv

journal_title

Science advances

authors

Dong J,Wang Z,Wang X,Song H,Liu Y,Wang Q

doi

10.1126/sciadv.aax9955

subject

Has Abstract

pub_date

2019-10-11 00:00:00

pages

eaax9955

issue

10

issn

2375-2548

pii

aax9955

journal_volume

5

pub_type

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