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Catalytic β C-H amination via an imidate radical relay.

ABSTRACT: The first catalytic strategy to harness imidate radicals for C-H functionalization has been developed. This iodine-catalyzed approach enables β C-H amination of alcohols by an imidate-mediated radical relay. In contrast to our first-generation, (super)stoichiometric protocol, this catalytic method enables faster and more efficient reactivity. Furthermore, lower oxidant concentration affords broader functional group tolerance, including alkenes, alkynes, alcohols, carbonyls, and heteroarenes. Mechanistic experiments interrogating the electronic nature of the key 1,5 H-atom transfer event are included, as well as probes for chemo-, regio-, and stereo-selectivity.

SUBMITTER: Stateman LM

PROVIDER: S-EPMC6419930 | biostudies-literature | 2019 Mar

REPOSITORIES: biostudies-literature

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Catalytic β C-H amination via an imidate radical relay.

Stateman Leah M LM Wappes Ethan A EA Nakafuku Kohki M KM Edwards Kara M KM Nagib David A DA

Chemical science 20190117 9

The first catalytic strategy to harness imidate radicals for C-H functionalization has been developed. This iodine-catalyzed approach enables β C-H amination of alcohols by an imidate-mediated radical relay. In contrast to our first-generation, (super)stoichiometric protocol, this catalytic method enables faster and more efficient reactivity. Furthermore, lower oxidant concentration affords broader functional group tolerance, including alkenes, alkynes, alcohols, carbonyls, and heteroarenes. Mec ...[more]

PMID: 30996986

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