TY - JOUR T1 - Catalysis of 3-pyrrolidinecarboxylic acid and related pyrrolidine derivatives in enantioselective anti-Mannich-type reactions: importance of the 3-acid group on pyrrolidine for stereocontrol. AU - Zhang,Haile, AU - Mitsumori,Susumu, AU - Utsumi,Naoto, AU - Imai,Masanori, AU - Garcia-Delgado,Noemi, AU - Mifsud,Maria, AU - Albertshofer,Klaus, AU - Cheong,Paul Ha-Yeon, AU - Houk,K N, AU - Tanaka,Fujie, AU - Barbas,Carlos F,3rd Y1 - 2007/12/29/ PY - 2008/1/1/pubmed PY - 2008/2/20/medline PY - 2008/1/1/entrez SP - 875 EP - 86 JF - Journal of the American Chemical Society JO - J Am Chem Soc VL - 130 IS - 3 N2 - The development of enantioselective anti-selective Mannich-type reactions of aldehydes and ketones with imines catalyzed by 3-pyrrolidinecarboxylic acid and related pyrrolidine derivatives is reported in detail. Both (3R,5R)-5-methyl-3-pyrrolidinecarboxylic acid and (R)-3-pyrrolidinecarboxylic acid efficiently catalyzed the reactions of aldehydes with alpha-imino esters under mild conditions and afforded anti-Mannich products with high diastereo- and enantioselectivities (anti/syn up to 99:1, up to >99% ee). For the reactions of ketones with alpha-imino esters, (R)-3-pyrrolidinecarboxylic acid was an efficient catalyst (anti/syn up to >99:1, up to 99% ee). Evaluation of a series of pyrrolidine-based catalysts indicated that the acid group at the beta-position of the pyrrolidine ring of the catalyst played an important role in forwarding the carbon-carbon bond formation and in directing anti-selectivity and enantioselectivity. SN - 1520-5126 UR - https://www.unboundmedicine.com/medline/citation/18163619/Catalysis_of_3_pyrrolidinecarboxylic_acid_and_related_pyrrolidine_derivatives_in_enantioselective_anti_Mannich_type_reactions:_importance_of_the_3_acid_group_on_pyrrolidine_for_stereocontrol_ DB - PRIME DP - Unbound Medicine ER -