Nucleophilic borylation of aldehydes and conjugated carbonyls: Applications to homologation and carbosilylation reactions

项目总结/摘要 主要研究者：蒂莫西·克拉克 圣地亚哥大学 助理PI：Gregory O 'Neil 西华盛顿大学 醛和共轭羰基的亲核硼基化：应用于同系化和 碳硅烷化反应 翻译后摘要：拟议的研究涉及利用铜的合成方法的发展- 醛和β，β-不饱和羰基的催化亲核硼基化。所得有机硼酸盐 酯将用作两种类型的合成反应的中间体：（1）碳硼的同系化 与络合物同系剂键合;（2）氧化反应，建立分子内羰基化反应，形成叔 醇的立体选择性。这两种方法制备合成有用的和高度取代的 有机中间体将简化对许多生物学相关目标的获取。的多功能性和 这些新方法提供的选择性将证明对于许多合成应用是上级的。 该项目的两个主要目标是： 1.利用醛硼基化/同系化来构建高度取代的有机硼酸酯， 邻接的立体中心。 2.开发使用系留硅烷的α-羟基酮的分子内碳硅烷化。

Project Summary/Abstract Lead-PI: Timothy Clark University of San Diego Sub-PI: Gregory O'Neil Western Washington University Title: Nucleophilic borylation of aldehydes and conjugated carbonyls: Applications to homologation and carbosilylation reactions Abstract: The proposed research involves the development of synthetic methods that utilize the copper- catalyzed nucleophilic borylation of aldehydes and ,-unsaturated carbonyls. The resulting organoboronate esters will be used as intermediates in two types of synthetic reactions: (1) homologation of the carbon–boron bond with complex homologating agents; (2) oxidation to set up intramolecular carbosilylations to form tertiary alcohols stereoselectively. These two approaches to preparing synthetically useful and highly-substituted organic intermediates will simplify access to a number of biologically relevant targets. The versatility and selectivities afforded by these new methods will prove superior for a number of synthetic applications. The two major aims of this project are: 1. Utilize aldehyde borylation/homologations to construct highly-substituted organoboronate esters with contiguous stereocenters. 2. Develop intramolecular carbosilylations of -hydroxyketones using tethered silanes.