Chemoselective Transformation of C-C Double Bonds by Using Transition-Metal Hediated Electrolysis

本课题研究了过渡金属催化碳碳双键的二羟基化和氨基羟基化反应。在一定量的铁氰化钾或碘的催化作用下，用锇和手性配体对烯烃进行不对称电-二羟基化反应，得到了手性二醇。该方法应用于手性紫草素的合成。研究了分子内杂原子对手性诱导的影响。对磺胺在aq. NaCl溶液中电解得到N，N-二氯-对甲苯磺酰胺。二氯磺胺在碱性水溶液中容易水解得到n -氯-对甲苯磺酰胺。在手性锇催化剂的作用下，用氯化对甲苯磺酰胺对烯烃进行不对称氨基羟基化反应，得到了手性胺类化合物。

In this project were investigated dihydroxylation and aminohydroxylation of carbon-carbon double bonds using transition-metal catalysts.Chiral diols were obtained from asymmetric electro-dihydroxylation of olefins using osmium and chiral ligands in the presence of a catalytic amount of potassium ferricyanide or iodine. This method was applied to the synthesis of chiral Shikonin. Effects of intramolecular hetero-atom on chiral induction was also studied.N,N-Dichloro-p-toluenesulfonamide was obtained from electrolysis of p-sulfonamide in aq. NaCl. The dichlorinated sulfonamide was easily hydrolyzed with a basic aqueous solution to give N-chloro-p-toluenesulfonamide. Asymmetric aminohydroxylation of olefins using the chlorinated p-toluenesulfonamide in the presence of chiral osmium catalyst proceeded smoothly to give chiral aminols in moderate yields and ees.