Development of Highly Stereoselective Reaction in Metal and Hetero-Atom Combined Reaction Filed

(1)将各种有机锂化合物与光学活性的2-甲酰基-1，3-氧硫杂环己烷衍生的亚胺或肼加成，得到了高非对映选择性的胺衍生物（de>99%），产率良好。(2)研究了光学活性2-丁烯酰基-1，3-氧硫杂环己烷的非对映选择性1，4-加成反应。在YbCl_3存在下，加入有机铜试剂，得到1，4-加成物。另一方面，在催化量的CuBr存在下用有机镁试剂处理，得到具有高非对映选择性的另一种非对映体。(3)三氟甲磺酸镧系元素被证明是各种胺与α，β-不饱和酯的1，4-加成反应的良好催化剂。该反应成功地应用于光学活性β-内酰胺的非对映选择性合成。(4)用烷基二氯化铝对2-烷基-2-甲酰胺进行了立体选择性烷基化反应。三烷基铝或烷基锰的氯化物与2-甲基-3-氧代酰胺的加成反应，得到了高立体选择性的3-羟基-2-甲基酰胺。

(1) An addition of various organolithium compounds to imine or hydrazine derived from optically active 2-formy1-1,3-oxathiane gave amine derivatives with high diastereoselectivity (>99% de) in good yields.(2) Diastereoselective 1,4-addition reaction of optically active 2-butenoy1-1,3-oxathiane was studied. The addition of organocupper reagent in the presence of YbCl_3 provided 1,4-adduct as a single diastercomeric compound. On the other hand, treatment with organomagnesium reagent in the presence of a catalytic amount of CuBr gave the other diastereomer with high diastereoselectivity.(3) Lanthanoid triflate proved to be a good catalyst for the 1,4-addition reaction of various amines to alpha, beta-unsaturated esters. The reaction was succesfully applied to a diastereoselective synthesis of optically active beta-lactams.(4) Stereoselective alkylation of 2-alky1-2-formylamide with alky1-aluminium dichloride was achieved. An addition of trialkylaluminium or alkylmanganese chloride to 2-methy1-3-oxo-amide gave the corresponding 3-hydroxy-2-methylamide with high stereoselectivity.