A General and Efficient Cobalt(II)-Based Catalytic System for Highly Stereoselective Cyclopropanation of Alkenes with alpha-Cyanodiazoacetates

作者：Zhu, Shifa; Xu, Xue; Perman, Jason A.; Zhang, X. Peter^*

来源：Journal of the American Chemical Society, 2010, 132(37): 12796-12799.

DOI：10.1021/ja1056246

• ASYMMETRIC CARBENE TRANSFER
• ENANTIOSELECTIVE CYCLOPROPANATION
• DIAZO REAGENTS
• AMINO-ACIDS
• SELECTIVITY
• CONSTRUCTION
• DERIVATIVES
• PORPHYRINS
• COMPLEXES
• OLEFINS

[Co(P1)], the cobalt(II) complex of the D-2-symmetric chiral porphyrin 3,5-Di(t)Bu-ChenPhyrin, is an effective catalyst for catalyzing asymmetric olefin cyclopropanation with the acceptor/acceptor-type diazo reagent alpha-cyanodiazoacetates. The [Co(P1)]-catalyzed reaction is versatile and suitable for both aromatic and aliphatic olefins with varied electronic properties, including electron-rich and -poor olefins. The Co(II)-based catalytic system can be operated in a one-time protocol under mild conditions, affording the desired cyclopropane products in high yields with both high diastereo- and enantioselectivity. The resulting enantiomerically enriched 1,1-cyclopropanenitrile esters provide convenient access to a number of densely functionalized chiral cyclopropane derivatives, including alpha-cyclopropyl-beta-amino acids.

• 出版日期2010-9-22
• 单位华南理工大学