Cobalt‐Catalyzed Enantioselective Alkenylation of Aldehydes

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.