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J Am Chem Soc. 2019 Jun 19;141(24):9548-9554. doi: 10.1021/jacs.9b04993. Epub 2019 Jun 10.

Bimetallic Radical Redox-Relay Catalysis for the Isomerization of Epoxides to Allylic Alcohols.

Author information

1
College of Chemistry , Fuzhou University , Fuzhou , 350116 , P.R. China.
2
Department of Chemistry and Chemical Biology , Cornell University , Ithaca , New York 14853 , United States.

Abstract

Organic radicals are generally short-lived intermediates with exceptionally high reactivity. Strategically, achieving synthetically useful transformations mediated by organic radicals requires both efficient initiation and selective termination events. Here, we report a new catalytic strategy, namely, bimetallic radical redox-relay, in the regio- and stereoselective rearrangement of epoxides to allylic alcohols. This approach exploits the rich redox chemistry of Ti and Co complexes and merges reductive epoxide ring opening (initiation) with hydrogen atom transfer (termination). Critically, upon effecting key bond-forming and -breaking events, Ti and Co catalysts undergo proton transfer/electron transfer with one another to achieve turnover, thus constituting a truly synergistic dual catalytic system.

PMID:
31180216
DOI:
10.1021/jacs.9b04993

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