Cobalt‐Catalyzed Enantioselective Alkenylation of Aldehydes

• Published in: Angewandte Chemie International Edition Vol. 63; no. 33; pp. e202405290 - n/a
• Main Authors: Lin, Chuiyi, Zhang, Jiwu, Sun, Zhao, Guo, Yinlong, Chong, Qinglei, Zhang, Zhihan, Meng, Fanke
• Format: Journal Article
• Language: English
• Published: Germany Wiley Subscription Services, Inc 12-08-2024
• Edition: International ed. in English
• Subjects: Alcohols; Aldehydes; alkenylation; allylic alcohol; axial stereogenicity; Catalysis; Cobalt; Cobalt compounds; Enantiomers; enantioselective catalysis; Halides; Reagents; alkenylation; axial stereogenicity; cobalt; allylic alcohol; enantioselective catalysis
• ISSN: 1433-7851; 1521-3773; 1521-3773
• DOI: 10.1002/anie.202405290

Catalytic enantioselective alkenylation of aldehydes with easily accessible alkenyl halides promoted by a chiral cobalt complex derived from a newly developed tridentate bisoxazolinephosphine is presented. Such processes represent an unprecedented reaction pathway for cobalt catalysis and a general approach that enable rapid construction of highly diversified enantioenriched allylic alcohols containing a 1,1‐, 1,2‐disubstituted and trisubstituted alkene as well as axial stereogenicity in up to 99 % yield and 99 : 1 er without the need of preformation of alkenyl–metal reagents. DFT calculations revealed the origin of enantioselectivity.
A new approach for highly efficient and enantioselective alkenylation of aldehydes promoted by an easily accessible cobalt‐based complex was developed. This protocol represents the first example of incorporating a wide range of alkenyl groups with diversified substitution patterns as well as axial stereogenicity into enantioenriched allylic alcohols.