Rhodium‐Catalyzed Atroposelective Access to Axially Chiral Olefins via C−H Bond Activation and Directing Group Migration
- 22 October 2021
- journal article
- research article
- Published by Wiley in Angewandte Chemie
- Vol. 61 (1), e202111860
- https://doi.org/10.1002/anie.202111860
Abstract
Axially chiral open-chain olefins represent an underexplored class of chiral platform. In this report, two classes of tetrasubstituted axially chiral acyclic olefins have been accessed in excellent enantioselectivity and regioselectivity via C-H activation of (hetero)arenes assisted by a migratable directing group en route to coupling with sterically hindered alkynes. The coupling of indoles bearing an N-aminocarbonyl directing group afforded C-N axially chiral acrylamides with assistance of a racemic zinc carboxylate additive. DFT studies suggest a β-nitrogen elimination-reinsertion pathway for the directing group migration. Meanwhile, the employment of N-phenoxycarboxamide delivered C-C axially chiral enamides via migration of the oxidizing directing group. Experimental studies suggest that in both cases the (hetero)arene substrate adopts a well-defined orientation during the C-H activation, which in turn determines the disposition of alkyne in migratory insertion. Synthetic applications of representative chiral olefins have been demonstrated.Keywords
Funding Information
- National Outstanding Youth Science Fund Project of National Natural Science Foundation of China (21525208)
- Young Scientists Fund (22101167)
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