TY - JOUR T1 - Direct catalytic asymmetric aldol-Tishchenko reaction. AU - Gnanadesikan,Vijay, AU - Horiuchi,Yoshihiro, AU - Ohshima,Takashi, AU - Shibasaki,Masakatsu, PY - 2004/6/24/pubmed PY - 2004/6/24/medline PY - 2004/6/24/entrez SP - 7782 EP - 3 JF - Journal of the American Chemical Society JO - J Am Chem Soc VL - 126 IS - 25 N2 - A direct catalytic asymmetric aldol reaction of propionate equivalent was achieved via the aldol-Tishchenko reaction. Coupling an irreversible Tishchenko reaction to a reversible aldol reaction overcame the retro-aldol reaction problem and thereby afforded the products in high enantio and diastereoselectivity using 10 mol % of the asymmetric catalyst. A variety of ketones and aldehydes, including propyl and butyl ketones, were coupled efficiently, yielding the corresponding aldol-Tishchenko products in up to 96% yield and 95% ee. Diastereoselectivity was generally below the detection limit of 1H NMR (>98:2). Preliminary studies performed to clarify the mechanism revealed that the aldol products were racemic with no diastereoselectivity. On the other hand, the Tishchenko products were obtained in a highly enantiocontrolled manner. SN - 0002-7863 UR - https://www.unboundmedicine.com/medline/citation/15212518/Direct_catalytic_asymmetric_aldol_Tishchenko_reaction_ DB - PRIME DP - Unbound Medicine ER -