4.6 Article

Cobalt-Catalyzed Intramolecular Hydroacylation Involving Cyclopropane Cleavage

Journal

CHEMISTRY-A EUROPEAN JOURNAL
Volume 26, Issue 37, Pages 8302-8307

Publisher

WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.202001223

Keywords

C-C bond cleavage; C-H activation; cobalt; cyclopropanes; hydroacylation

Funding

  1. Ministry of Education (Singapore)
  2. Nanyang Technological University [MOE2016-T2-2-043, RG114/18]
  3. JSPS KAKENHI [JP17KT0011]
  4. National Natural Science Foundation of China [21901043]

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A simple cobalt-diphosphine catalyst has been found to efficiently promote intramolecular cyclization ofortho-cyclopropylvinyl- and cyclopropylidenemethyl-substituted benzaldehydes into benzocyclooctadienone and benzocycloheptadienone derivatives, respectively. This ring-opening hydroacylation likely involves aldehyde C-H oxidative addition, olefin insertion, cyclopropane cleavage by beta-carbon elimination, and C-C bond-forming reductive elimination, as was supported by mechanistic experiments and DFT calculations.

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