Direct Catalytic Asymmetric Mannich-Type Reaction of b-Keto Phosphonate Using a Dinuclear Ni2-Schiff Base Complex.

[摘要]：Direct catalytic asym. Mannich-type reactions of b-keto phosphonates are described. A homodinuclear Ni2-Schiff base complex promoted the reaction at 0? giving b-amino phosphonates in up to 90% yield, 20:1 dr, and 99% ee. Control expts. suggested that two Ni metals are important for achieving high yield and stereoselectivity. Thus, Ni2-Schiff base catalyzed and 13X MS promoted Mannich-type reaction of Boc-N:CHC6H4Cl-4 with b-keto phosphonate I in PhMe at 0?gave 43% b-amino phosphonate II (crystal structure) in 48h with 84% enantiomeric excess.

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