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

项目摘要/摘要 主演：蒂莫西·克拉克 圣地亚哥大学 次品派：格雷戈里·奥尼尔 西华盛顿大学 标题：醛和共轭羰基的亲核硼化反应：在同系化和 碳硅化反应 摘要：拟议的研究涉及开发利用铜的合成方法。 催化的醛和，不饱和羰基的亲核硼化反应。由此产生的有机硼 酯将被用作两类合成反应的中间体：(1)碳-硼的同系化 与复杂的同系物结合；(2)氧化以建立分子内的碳硅化反应形成叔基 醇类化合物的立体选择性。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相关靶标的获取。多功能性和 事实证明，这些新方法提供的选择性将在许多合成应用中发挥更好的作用。 该项目的两个主要目标是： 1.利用醛的硼化/同系物合成高取代的有机硼酸酯 连续的立体中心。 2.发展了-羟基酮的分子内硅烷化反应。

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.