Selective Synthesis through Dehydrogenative Silylation with Optically Active Gold(I) Complex

光学活性化合物的高效合成是有机合成中的一个重要问题。此外，开发高效利用资源和减少废物的新反应已成为非常重要的课题。本研究考察了光学活性金(I)配合物与脱氢硅烷化反应动力学拆分手性醇的新方法。作为初步实验，合成了具有不同空间体积的黄膦配体，并研究了这些配体与金(I)催化的脱氢硅基化反应。空间受阻配体表现出较高的活性。其次，利用手性膦配体对手性醇的动力学拆分进行了测试。为了开发更高效的金(I)催化拆分催化剂，合成了一种有望作为催化中间体的金(I)氢化物，并对其进行了表征。虽然金(I)氢化物以前从未在溶液中被表征过，但研究人员发现，金氢化物分泌物是在金(I)催化的醇的脱氢硅化反应中产生的。用氢、磷、碳、核磁共振和电喷雾质谱仪对金(I)氢化物进行了表征。

Efficient synthesis of optically active compounds is important issue in organic synthesis. In addition, development of new reactions for efficient utilization of resources and reduction of wastes have become very important subject. In this study, the new methods involving kinetic resolution of chiral alcohols through dehydrogenative silylation with optically active gold(I) complexes were examined.As a preliminary experiment, xantphos-type ligands that have different steric bulk were prepared and the gold(I)-catalyzed dehydrogenative silylation with these ligands was studied. The sterically hindered ligands showed high activities. Next, kinetic resolutions of chiral alcohols were tested by using chiral phosphine ligands. Although the optically active alcohols were obtained, the enantiomeric purities of the resultant products were low.In order to develop more efficient gold(I) catalysts for kinetic resolution, synthesis and characterization of a gold(I) hydride compound, which is expected to be a key intermediate of catalysis, were investigated. Although gold(I) hydride compounds had never been characterized in solution before, the researcher found that the gold hydride secrecies were generated in the gold(I)-catalyzed dehydrogenative silylation of alcohols. The gold(I) hydride species were characterized by H, P, C, NMR and ESI-Mass.