Authors: Huw M. L. Davies , Paul R. Bruzinski , Debra H. Lake , Norman Kong , and Michael J. Fall
J. Am. Chem. Soc.,
1996, 118 (29), 6897–6907
The rhodium N-(arylsulfonyl)prolinate catalyzed decomposition of vinyldiazomethanes in the presence of alkenes leads to a very general method for the synthesis of functionalized cyclopropanes in a highly diastereoselective and enantioselective mode. A detailed study was undertaken to determine the key factors that control the enantioselectivity of this process. The highest levels of enantioselectivity were obtained using cyclic N-(arylsulfonyl)amino acids as ligands for the dirhodium catalyst, and the optimized catalyst was tetrakis[N-[(4-dodecylphenyl)sulfonyl]-(L)-prolinato]dirhodium. The carbenoid structure has a critical effect on the degree of asymmetric induction, and the combination of a small electron-withdrawing group such as a methyl ester and an electron-donating group such as vinyl or phenyl resulted in the highest levels of enantioselectivity. The use of electron neutral alkenes and pentane as solvent also enhanced the enantioselectivity of the process. The synthetic utility of this chemistry was illustrated by its application to the synthesis of all four stereoisomers of 2-phenylcyclopropan-1-amino acid. The occurrence of the highly stereoselective cyclopropanations was rationalized by a model in which the ligands were considered to adopt a D2 symmetric arrangement.