Highly diastereoselective synthesis of α-difluoromethyl amines from N-tert-butylsulfinyl ketimines and difluoromethyl phenyl sulfone.
The first highly efficient and stereoselective difluoromethylation of structurally diverse N-tert-butylsulfinyl ketimines has been achieved with an in situ generated PhSO(2)CF(2)(-) anion, which provides a powerful synthetic method for the preparation of a variety of structurally diverse homochiral α-difluoromethyl tertiary carbinamines, including α-difluoromethyl allylic amines and α-difluoromethyl propargylamines. The stereocontrol mode of the present diastereoselective difluoromethylation of ketimines was found to be different from that of other known fluoroalkylations of N-tert-butylsulfinyl aldimines, which suggests that a cyclic six-membered transition state may be involved in the reaction.
Liu
Jun
J
Key Laboratory of Organofluorine Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Ling-Ling Road, Shanghai 200032, China.
Hu
Jinbo
J
D000588:Amines / Q000138:chemical synthesis* / Q000737:chemistry; D020650:Combinatorial Chemistry Techniques; D018360:Crystallography, X-Ray; D007097:Imines / Q000737:chemistry*; D008968:Molecular Conformation; D015394:Molecular Structure; D009570:Nitriles / Q000737:chemistry*; D010293:Pargyline / Q000031:analogs & derivatives* / Q000138:chemical synthesis / Q000737:chemistry; D011437:Propylamines / Q000138:chemical synthesis* / Q000737:chemistry; D013237:Stereoisomerism; D013450:Sulfones / Q000737:chemistry*; D013454:Sulfoxides / Q000737:chemistry*
D000588:Amines; D007097:Imines; D009570:Nitriles; D011437:Propylamines; D013450:Sulfones; D013454:Sulfoxides; C542835:ketimine; C009054:propargylamine; D010293:Pargyline