Allene Directed Asymmetric Synthesis

本研究的重点是考察手性联烯基锡、硼、钛、铬、钯等金属试剂的合成用途。将特别关注SE对醛的加成反应，以此作为一种富含对映体的丙叉醇和烯丙醇的途径。需要解决的问题包括：手性烯丙基和炔丙基有机金属化合物的构象和区域化学稳定性，涉及这些试剂的SE‘加成反应的立体化学和区域化学，配体对这些试剂与SE’加成反应的对映体选择性和区域选择性的影响，以及这些试剂在天然产物合成中的可能应用。通过这次更新的奖项，有机和高分子化学计划支持弗吉尼亚大学化学系的詹姆斯·A·马歇尔博士的研究。马歇尔教授将专注于开发利用锡、硼、钛、铬和钯的手性烯基试剂制备手性碳化合物的新合成方法。这些新型中间体有潜力用于构建制药和农业行业感兴趣的天然产品。

The focus of this research is the examination of the synthetic utility of chiral allenylmetallic reagents of tin, boron, titanium, chromium and palladium. Particular attention will be focused on SE' additions to aldehydes as a route to enantioenriched propargylic and allenic carbinols. Among the issues to be addressed are: The conformational and regiochemical stability of chiral allenyl and propargyl organometallics, the stereochemistry and regiochemistry of SE' additions involving these reagents, the effect of ligands on the enantioselectivity and regioselectivity of SE' additions with these reagents and the possible applications of these reagents in natural products synthesis.With this renewal award, the Organic and Macromolecular Chemistry Program is supporting the research of Dr. James A. Marshall of the Department of Chemistry at the University of Virginia. Professor Marshall will focus his work on the development of new synthetic methodology for the preparation of chiral carbon compounds by the use of chiral allenyl reagents of tin, boron, titanium, chromium and palladium. These novel intermediates have potential for use in the construction of natural products of interest to the pharmaceutical and agricultural industries.