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 Advjournal_title
Science advancesauthors
Dong J,Wang Z,Wang X,Song H,Liu Y,Wang Qdoi
10.1126/sciadv.aax9955subject
Has Abstractpub_date
2019-10-11 00:00:00pages
eaax9955issue
10issn
2375-2548pii
aax9955journal_volume
5pub_type
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