Highly Enantioselective Cyclopropanation of Styrenes and Diazoacetates Catalyzed by 3-Oxobutylideneaminatocobalt(II) Complexes, Part 1. Designs of Cobalt Complex Catalysts and the Effects of Donating Ligands

Highly enantioselective cyclopropanation of styrene derivatives and diazoacetates was effectively catalyzed by reasonably designed 3-oxobutylideneaminatocobalt(II) complexes, whose ligands were prepared from 1,2-dimesitylethylenediamine and alkyl 3-oxobutanoates. The steric demand of the diamine unit of the complexes seriously influenced the enantioselectivity, and the ester groups on their side chains somewhat improved the trans-selectivity. Addition of a catalytic amount of N-methylimidazole significantly accelerated the reaction and enhanced the enantioselectivity due to its coordination to the center cobalt atom of the complex as an axial ligand. Alcoholic or aqueous alcoholic solvents were also effective particularly for the cyclopropanation of 1-substituted 1-phenylethylenes to achieve high enantioselectivity in aqueous methanol.