3854-52-2Relevant articles and documents
Rhodium(I)-Catalyzed Enantioselective Cyclization of Enynes through Site-Selective C(sp 3)-H Bond Activation Triggered by Formation of Rhodacycle
Oonishi, Yoshihiro,Sakamoto, Shunki,Agata, Shuya,Sato, Yoshihiro
, p. 2976 - 2983 (2021)
Rhodium(I)-catalyzed enantioselective cyclization of enynes through C(sp 3)-H bond activation was investigated. It was found that the cyclization of enynes having a tert -butyl moiety on the alkene afforded a spirocyclic compound (up to 92% ee), while the cyclization of enynes having an isopropyl or an ethyl group on the alkene gave a cyclic diene (up to 98% ee). Furthermore, an intermolecular competition reaction using a deuterium-labeled substrate revealed that C(sp 3)-H bond activation was one of the key steps, having a high energy barrier, in this cyclization.
Pd-Catalyzed Asymmetric Acyl-Carbamoylation of an Alkene to Construct an α-Quaternary Chiral Cycloketone
Liu, Min,Wang, Xing,Guo, Ziqiong,Li, Hanyuan,Huang, Wei,Xu, Hui,Dai, Hui-Xiong
supporting information, p. 6299 - 6304 (2021/08/30)
Herein, we report the palladium-catalyzed asymmetric acyl-carbamoylation of an alkene by employing thioesters as the acyl electrophiles and t-BuNC as the carbamoyl reagent, affording an α-quaternary chiral cycloketone in synthetically useful yields with excellent enantioselectivity. The reaction proceeded via asymmetric 1,2-migratory insertions of acyl-Pd into alkenes and subsequent migratory insertion of isocyanides into C(sp3)-PdII. The product could be diversified to some valuable skeletons with retention of enantiopurity, demonstrating the synthetic utility of this protocol.
Organic base-catalysed solvent-tuned chemoselective carbotrifluoromethylation and oxytrifluoromethylation of unactivated alkenes
Yang, Ning-Yuan,Li, Zhong-Liang,Ye, Liu,Tan, Bin,Liu, Xin-Yuan
, p. 9052 - 9055 (2016/07/21)
An unprecedented and efficient organic base-catalysed highly chemoselective carbo- and oxytrifluoromethylation of unactivated alkenes with Togni's reagent was developed. The switchable chemoselectivity was tuned by simply changing the organic base catalyst and solvent. Mechanistic studies indicated that a radical cyclization pathway for carbotrifluoromethylation in DMSO and a carbocation pathway for oxytrifluoromethylation in DCE were probably involved.