Vitamin B12 derivatives as natural asymmetric catalysts: enantioselective cyclopropanation of alkenes.
Vitamin B(12) derivatives were found for the first time to be general and efficient catalysts for asymmetric cyclopropanation of alkenes with ethyl diazoacetate (EDA). Among several common derivatives, aquocobalamin (B(12a)) was shown to be the most effective catalyst for a variety of alkenes, providing cis-dominant cyclopropanes in excellent yields and moderate enantioselectivity. Reactivity studies under different conditions suggest that the active species in the proposed catalytic cycle is the base-on cob(II)alamin (B(12r)) that is generated possibly via in situ reduction of B(12a) by EDA.
Chen
Ying
Y
Department of Chemistry, University of Tennessee, Knoxville, Tennessee 37996-1600, USA.
Zhang
X Peter
XP
D000475:Alkenes / Q000737:chemistry*; D002264:Carboxylic Acids / Q000138:chemical synthesis*; D002384:Catalysis; D020650:Combinatorial Chemistry Techniques; D003521:Cyclopropanes / Q000737:chemistry*; D003979:Diazonium Compounds / Q000737:chemistry; D007202:Indicators and Reagents; D015394:Molecular Structure; D013237:Stereoisomerism; D014805:Vitamin B 12 / Q000031:analogs & derivatives* / Q000737:chemistry*
D000475:Alkenes; D002264:Carboxylic Acids; D003521:Cyclopropanes; D003979:Diazonium Compounds; D007202:Indicators and Reagents; C043960:aquacobalamin; C032111:diazoacetic ester; D014805:Vitamin B 12