Mechanistic investigation of a novel vitamin B12-catalyzed carbon-carbon bond forming reaction, the reductive dimerization of arylalkenes

Justin Shey, Chris M. McGinley, Kevin M. McCauley, Anthony S. Dearth, Brian T. Young, Wilfred Adrianus van der Donk

Research output: Contribution to journalArticlepeer-review

Abstract

In the presence of catalytic vitamin B12 and a reducing agent such as Ti(III)citrate or Zn, arylalkenes are dimerized with unusual regioselectivity forming a carbon-carbon bond between the benzylic carbons of each coupling partner. Dimerization products were obtained in good to excellent yields for mono- and 1,1-disubstituted alkenes. Dienes containing one aryl alkene underwent intramolecular cyclization in good yields. However, 1,2-disubstituted and trisubstituted alkenes were unreactive. Mechanistic investigations using radical traps suggest the involvement of benzylic radicals, and the lack of diastereoselectivity in the product distribution is consistent with dimerization of two such reactive intermediates. A strong reducing agent is required for the reaction and fulfills two roles. It returns the Co(II) form of the catalyst generated after the reaction to the active Co(I) state, and by removing Co(II) it also prevents the nonproductive recombination of alkyl radicals with cob(II)alamin. The mechanism of the formation of benzylic radicals from arylalkenes and cob(I)alamin poses an interesting problem. The results with a one-electron transfer probe indicate that radical generation is not likely to involve an electron transfer. Several alternative mechanisms are discussed.

Original languageEnglish (US)
Pages (from-to)837-846
Number of pages10
JournalJournal of Organic Chemistry
Volume67
Issue number3
DOIs
StatePublished - Feb 8 2002

ASJC Scopus subject areas

  • Organic Chemistry

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