期刊
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
卷 59, 期 50, 页码 22706-22713出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.202010832
关键词
asymmetric catalysis; C-H activation; enynes; lactams; rhodium
资金
- NSFC [21525208]
- China Postdoctoral Science Foundation [2019M653531]
- SNNU
We report chiral Rh(III)cyclopentadienyl-catalyzed enantioselective synthesis of lactams and isochromenes through oxidative [4+1] and [5+1] annulation, respectively, between arenes and 1,3-enynes. The reaction proceeds through a C-H activation, alkenyl-to-allyl rearrangement, and a nucleophilic cyclization cascade. The mechanisms of the [4+1] annulations were elucidated by a combination of experimental and computational methods. DFT studies indicated that, following the C-H activation and alkyne insertion, a Rh(III)alkenyl intermediate undergoes delta-hydrogen elimination of the allylic C-H via a six-membered ring transition state to produce a Rh(III)enallene hydride intermediate. Subsequent hydride insertion and allyl rearrangement affords several rhodium(III) allyl intermediates, and a rare Rh-III eta(4)ene-allyl species with pi-agostic interaction undergoes SN2 '-type external attack by the nitrogen nucleophile, instead of C-N reductive elimination, as the stereodetermining step.
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