Study on Asymmetric Synthesis and Application to physiological Active Compound

1.用1-氯代烷基对甲苯亚砜不对称合成某些羰基化合物。研究了光学活性1-氯烷基对甲苯基亚砜的实际合成方法，并成功地实现了光学活性环氧化物、烯丙醇、氨基醛和氮杂环丙烷的不对称合成。(1)以光学活性1-氯烷基对甲苯基亚砜为起始原料，不对称合成了α-羟基羧酸、酯、酰胺、乙炔、丙叉醇。(2)研究了不对称Favorskii重排反应合成光学活性氨基化合物。(3)研究了环烯丙基环丙烷与环烷基环芳烃的环合反应，并将其应用于稠环3-甲基呋喃的合成。欧米伽甲酰基烯丙基硅烷的非对映选择性环化为双环α-亚甲基-伽马-内酯。(1)利用手性辅助基团进行非对映选择性环化。(2)以(+)-香茅醛为起始原料，非对映选择性地合成顺式和反式-对甲内酯。(3)海洋天然产物西柏烯内酯的全合成成功。

1. Asymmetric Synthesis of Some Carbonyl Compounds Using 1-Chloroalkyl p-Tolyl Sulfoxides. Practical synthetic procedure of optical active 1-chloroalkyl p-tolyl sulfoxides was investigated, and asymmetric synthesis of optical active epoxides, allylic alcohols, amino-aldehydes, and aziridines had been sucseccful.(1) Asymmetric synthesis of alpha-hydroxy-carboxylic acids, esters, amides, acetylenes, propargylic alcohols starting from the optical active 1-chloroalkyl p-tolyl sulfoxides were successful.(2) Synthesis of optical active amido compounds by the asymmetric Favorskii rearrangement was investigated.(3) Synthesis of methylenecyclopropane spiro linked with cycloalkanes via cyclization of allylic epoxides was investigated, its application to a sythesis of fused rings 3-methylfuranes.2. Diastereoselective cyclization of omega-formylated allylic silanes into bicyclic alpha-methylene-gamma-lactones.(1) Diastereoselective cyclization of omega-formylated allylic silanes using chiral auxiliary groups was investigated.(2) Diastereoselective sythesis of cis and trans-p-methanolides starting from (+)-citronellal was sucessful.(3) Total synthesis of cembrenolide, marine natural product, was successful.