Mapping the active site in a chemzyme: diversity in the N-substituent in the catalytic asymmetric aziridination of imines.
The active site of the aziridination catalyst derived from either the VANOL or VAPOL ligand and B(OPh)(3) is larger than expected and can accommodate not only significant substitution on the diarylmethyl unit of the imine but also that alkyl (but not perfluorylalkyl) substituents on the aryl groups lead to enhanced rates and enantioselection. The screen of diarylmethyl N-substituents on the imine revealed that the 3,5-di-tert-butyldianisylmethyl group (BUDAM) gave exceptionally high asymmetric inductions for imines of aryl aldehydes.
Zhang
Yu
Y
Department of Chemistry, Michigan State University, East Lansing, Michigan 48824,USA.
Lu
Zhenjie
Z
Desai
Aman
A
Wulff
William D
WD
D001388:Aziridines / Q000737:chemistry*; D002384:Catalysis; D020134:Catalytic Domain; D004583:Electrons; D007097:Imines / Q000737:chemistry*; D008968:Molecular Conformation; D009281:Naphthalenes / Q000737:chemistry; D009584:Nitrogen / Q000737:chemistry*
D001388:Aziridines; D007097:Imines; D009281:Naphthalenes; C530040:VANOL ligand; C033132:aziridine; D009584:Nitrogen