Development of ruthenium catalysts for the enantioselective synthesis of P-stereogenic phosphines via nucleophilic phosphido intermediates

被引：0
|
作者：
Chan, Vincent S. [1 ]
Chiu, Melanie [1 ]
Bergman, Robert G. [1 ]
Toste, F. Dean [1 ]
机构：
[1] Department of Chemistry, University of California, Berkeley, CA 94720, United States
来源：
Journal of the American Chemical Society | 2009年 / 131卷 / 16期
关键词：
This work details the development of ruthenium(ll) catalysts for the enantioselective alkylation of chiral racemic secondary phosphines. The reactions proceed through the intermediacy of nucleophilic phosphido species; which have low barriers to pyramidal inversion; this allows for a dynamic kinetic asymmetric alkylation. The initially discovered [((R)-/Pr-PHOX) 2Ru(H)][BPh 4] (6) catalyst was found to be effective in the reaction with benzylic chlorides; moreover, the alkylation displayed an unusual temperature dependence. However, the limited scope of alkylation of 6 motivated further studies which led to the development of two complementary chiral mixed ligand Ru(ll) catalysts of type [L 1L 2Ru(H)] +. These catalysts were derived from a combination of one chiral and one achiral ligand, where a synergistic interaction of the two ligands creates an effective asymmetric environment around the ruthenium center. The (R)-MeO-BiPHEP/dmpe (dmpe = 1,2-bis(dimethylphosphino)ethane) catalyst (10) was found to be effective for the asymmetric alkylation of benzylic chlorides, while the (R)-DIFLUORPHOS/dmpe catalyst (11) was optimal for the nucleophilic substitution of less activated alkyl bromides; the scope of the respective catalysts was also explored. © 2009 American Chemical Society;
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页码：6021 / 6032
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