Stereoselective aldol reactions of dihydroxyacetone derivatives catalyzed by chiral Zn2+ complexes |
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| Authors: | Masato Yasuda Yutaka Saga Takuya Tokunaga Susumu Itoh Shin Aoki |
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| Affiliation: | 1. Faculty of Pharmaceutical Sciences, Tokyo University of Science, 2641 Yamazaki, Noda, Chiba 278-8510, Japan;2. API Department, CMC Center, Kaken Pharmaceutical Co., LTD, 301 Gensuke, Fujieda, Shizuoka 426-8646, Japan;3. Imaging Frontier Center, Research Institute for Science and Technology, Tokyo University of Science, 2641 Yamazaki, Noda, Chiba 278-8510, Japan |
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| Abstract: | The direct aldol reaction between a protected dihydroxyacetone derivative and 4-nitrobenzaldehyde catalyzed by chiral Zn2+ complexes of 1-(n-carboxylalkyl)-7-aminoacyl-1,4,7,10-tetraazacyclododecane is reported. New Zn2+ complexes containing l-histidine and carboxylalkyl chains that mimic a class II aldolase, carboxypeptidase A and a serine protease were designed and synthesized. Syn-aldol products were mainly formed by an aldol reaction of acetonide-protected dihydroxyacetone with benzaldehydes and other benzaldehydes in N-methylpyrrolidone (NMP)/alcohol (MeOH, EtOH or 2-PrOH) in good yields with a high degree of diastereo- and enantioselectivity (56%～quant., 57～>99% ee). Mechanistic aspect based on ESI-HRMS, elemental analysis and pH titrations of model ligands is also discussed. |
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| Keywords: | Aldol reaction Asymmetric catalysis Enzyme models Macrocyclic ligands Zinc |
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