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- Title
Palladium(II)‐Catalyzed Enantioselective Arylation of Unbiased Methylene C(sp<sup>3</sup>)−H Bonds Enabled by a 2‐Pyridinylisopropyl Auxiliary and Chiral Phosphoric Acids.
- Authors
Yan, Sheng‐Yi; Han, Ye‐Qiang; Yao, Qi‐Jun; Nie, Xing‐Liang; Liu, Lei; Shi, Bing‐Feng
- Abstract
Abstract: Enantioselective functionalizations of unbiased methylene C(sp3)−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 β‐C(sp3)−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‐C2‐symmetric CPA is crucial for effective stereocontrol. A broad range of aliphatic carboxylic acids and aryl bromides can be used, providing β‐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.
- Subjects
PALLADIUM; PHOSPHORIC acid; CARBOXYLIC acid derivatives; ARYLATION; ARYL bromides; CARBOXYLIC acids
- Publication
Angewandte Chemie, 2018, Vol 130, Issue 29, p9231
- ISSN
0044-8249
- Publication type
Article
- DOI
10.1002/ange.201804197