STEREOSELECTIVE SYNTHESIS WITH TRANSITION METAL ENOLATES

由于合成有机化合物在医学和生物医学中的重要性， 生物化学研究，有机合成是健康的基础 以理工科为重 有机合成的一个重要方面是立体选择性。 在 在过去的十年里，化学家们已经开发了许多方法， 手性化合物的对映选择性制备。 然而，有效 实现催化不对称诱导的方法仍然很少。 的 这些方法中最重要的两种， 通过烯烃加氢制备氨基酸和对映选择性 不饱和醇的环氧化，不涉及碳-碳键 阵 没有催化的，对映选择性的版本存在的一个 最重要的合成反应，羟醛加成反应。 在 本项目建议寻找这样的方法。 研究将 开始与准备和表征的一系列过渡 金属烯醇化物。 这些材料与各种有机物的反应 底物，包括醛，酮，腈，酯，烯酮， 将研究异腈、偶氮化合物、烯烃和炔烃。 将尝试建立催化循环，使得期望的 可以仅用少量的活性化合物进行转化， 催化 最后，将研究手性配体的影响， 实现催化不对称诱导的最终目标。

Because of the importance of synthetic organic compounds in medicine and in biochemical research, organic synthesis is fundamental to the health sciences. A crucial aspect of organic synthesis is stereoselectivity. In the last decade, chemists have developed a number of methods that allow the enantioselective preparation of chiral compounds. However, effective methods for achieving catalytic asymmetric induction are still rare. The two most important of these methods, the enantioselective synthesis of animo acids by hydrogenation of alkenes and the enantioselective epoxidation of unsaturated alcohols, do not involve carbon-carbon bond formation. No catalytic, enantioselective versions exist for the one of the most important synthetic reactions, the aldol addition reaction. In this project, it is proposed to search for such a method. Research will begin with the preparation and characterization of a series of transition metal enolates. The reactions of these materials with various organic substrates, including aldehydes, ketones, nitriles, esters, enones, isonitriles, azo compounds, alkenes, and alkynes, will be investigated. Attempts will be made to establish catalytic cycles, so that desirable transformations may be carried out with only small amounts of active catalyst. Finally, the effects of chiral ligands will investigated, with the ultimate goal of achieving catalytic asymmetric induction.