One-pot enantioselective aziridination of olefins catalyzed by a copper(I) complex of a novel diimine ligand by using PhI(OAc)(2) and sulfonamide as nitrene precursors.
A novel chiral C(2)-symmetric 1,4-diamine with multistereogenic centers at the backbone of the ligand has been synthesized from cheap natural product D-mannitol through multistep transformations. Its diimine derivative (3 a) was found to be highly effective for the enantioselective control of the copper-catalyzed asymmetric aziridination of olefin derivatives with PhI==NTs as the nitrene source, affording the corresponding N-sulfonylated azirindine derivatives in good to excellent yields with up to 99 % ee (ee=enantiomeric excess). The catalyst system discovered in the present work was also extended to a one-pot enantioselective aziridination by using sulfonamide/iodobenzene diacetate as the nitrene source. In this case, most reactions proceeded smoothly to give the corresponding products in moderate yields with good to excellent enantiomeric excesses (75-96 % ee).
Wang
Xisheng
X
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 354 Fenglin Road, Shanghai 200032, P. R. China. kding@mail.sioc.ac.cn
Ding
Kuiling
K
D000475:Alkenes / Q000737:chemistry*; D001388:Aziridines / Q000737:chemistry*; D002384:Catalysis; D003300:Copper / Q000737:chemistry*; D007097:Imines / Q000737:chemistry*; D008024:Ligands; D013237:Stereoisomerism; D013449:Sulfonamides / Q000737:chemistry
D000475:Alkenes; D001388:Aziridines; D007097:Imines; D008024:Ligands; D013449:Sulfonamides; C017621:phenylnitrene; C033132:aziridine; D003300:Copper