Directed Cobalt-Catalyzed anti-Markovnikov Hydroalkylation of Unactivated Alkenes Enabled by "Co-H" Catalysis

Dandan Yang; Hai Huang; Meng-Hui Li; Xiao-Ju Si; He Zhang; Jun-Long Niu; Mao-Ping Song

doi:10.1021/acs.orglett.0c01365

Directed Cobalt-Catalyzed anti-Markovnikov Hydroalkylation of Unactivated Alkenes Enabled by "Co-H" Catalysis

Org Lett. 2020 Jun 5;22(11):4333-4338. doi: 10.1021/acs.orglett.0c01365. Epub 2020 May 13.

Authors

Dandan Yang¹, Hai Huang², Meng-Hui Li¹, Xiao-Ju Si¹, He Zhang¹, Jun-Long Niu¹, Mao-Ping Song¹

Affiliations

¹ Green Catalysis Center, and College of Chemistry, Zhengzhou University, Zhengzhou 450001, P. R. China.
² Jiangsu Key Laboratory of Advanced Catalytic Materials & Technology, School of Petrochemical Engineering, Changzhou University, Changzhou 213164, China.

PMID: 32401533
DOI: 10.1021/acs.orglett.0c01365

Abstract

The earth-abundant cobalt-catalyzed anti-Markovnikov hydroalkylation of unactivated alkenes with oxime esters was achieved by introducing an 8-aminoquinoline directing group on the alkenes. The catalytic system, consisting of commercially available Co(acac)₃ and PhMeSiH₂, enables the construction of unfunctionalized C(sp³)-C(sp³) bonds and features exclusive anti-Markovnikov selectivity, good functional group tolerance, and the avoidance of an extra ligand, oxidant, or base. Mechanistic insight into this new catalytic system indicates the involvement of both alkyl radical and cobalt hydride intermediates.