Journal
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
Volume 57, Issue 29, Pages 9093-9097Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.201804197
Keywords
bidentate auxiliaries; C-H activation; cooperative effects; enantioselectivity; palladium
Categories
Funding
- NSFC [21772170, 21572201, 21422206]
- National Basic Research Program of China [2015CB856600]
- Fundamental Research Funds for the Central Universities [2018XZZX001-02]
Ask authors/readers for more resources
Enantioselective functionalizations of unbiased methylene C(sp(3))-H bonds of linear systems by metal insertion are intrinsically challenging and remain a largely unsolved problem. Herein, we report a palladium(II)-catalyzed enantioselective arylation of unbiased methylene -C(sp(3))-H bonds enabled by the combination of a strongly coordinating bidentate PIP auxiliary with a monodentate chiral phosphoric acid (CPA). The synergistic effect between the PIP auxiliary and the non-C-2-symmetric CPA is crucial for effective stereocontrol. A broad range of aliphatic carboxylic acids and aryl bromides can be used, providing -arylated aliphatic carboxylic acid derivatives in high yields (up to 96%) with good enantioselectivities (up to 95:5 e.r.). Notably, this reaction also represents the first palladium(II)-catalyzed enantioselective C-H activation with less reactive and cost-effective aryl bromides as the arylating reagents. Mechanistic studies suggest that a single CPA is involved in the stereodetermining C-H palladation step.
Authors
I am an author on this paper
Click your name to claim this paper and add it to your profile.
Reviews
Recommended
No Data Available