Yang Dandan, Huang Hai, Li Meng-Hui, Si Xiao-Ju, Zhang He, Niu Jun-Long, Song Mao-Ping
Green Catalysis Center, and College of Chemistry, Zhengzhou University, Zhengzhou 450001, P. R. China.
Jiangsu Key Laboratory of Advanced Catalytic Materials & Technology, School of Petrochemical Engineering, Changzhou University, Changzhou 213164, China.
Org Lett. 2020 Jun 5;22(11):4333-4338. doi: 10.1021/acs.orglett.0c01365. Epub 2020 May 13.
The earth-abundant cobalt-catalyzed -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) and PhMeSiH, enables the construction of unfunctionalized C(sp)-C(sp) bonds and features exclusive -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.
通过在烯烃上引入8-氨基喹啉导向基团，实现了地球丰富的钴催化未活化烯烃与肟酯的马氏氢烷基化反应。由市售的Co(acac)和PhMeSiH组成的催化体系能够构建未官能团化的C(sp³)-C(sp³)键，具有独特的马氏选择性、良好的官能团耐受性，并且无需额外的配体、氧化剂或碱。对这一新催化体系的机理研究表明，烷基自由基和氢化钴中间体均参与其中。
