Synthesis of Axially Chiral Styrenes through Pd‐Catalyzed Asymmetric C−H Olefination Enabled by an Amino Amide Transient Directing Group
Authors:
- 3 February 2020
- journal article
- research article
- Published by Wiley in Angewandte Chemie International Edition
- Vol. 59 (16) , 6576-6580
Abstract
The atroposelective synthesis of axially chiral styrenes remains a formidable challenge due to their relatively lower rotational barriers compared to the biaryl atropoisomers. Herein, we describe the construction of axially chiral styrenes through PdII‐catalyzed atroposelective C−H olefination, using a bulky amino amide as a transient chiral auxiliary. Various axially chiral styrenes were produced with good yields and high enantioselectivity (up to 95 % yield and 99 %ee). Carboxylic acid derivatives of the resulting axially chiral styrenes showed superior enantiocontrol over the biaryl counterparts in CoIII‐catalyzed enantioselective C(sp3)−H amidation of thioamide. Mechanistic studies suggest that C−H cleavage is the enantioselectivity‐determining step.Keywords
Funding Information
- National Natural Science Foundation of China (21772170; 21925109)
- Fundamental Research Funds for the Central Universities (2018XZZX001-02)
- Natural Science Foundation of Zhejiang Province (LR17B020001)
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