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.
Compounds that contain carbon?boron bonds are versatile synthetic intermediates that can be used to access a large array of functional groups that are often found in pharmaceutical drugs and functional materials. This project will utilize nucleophilic boron sources to access unique organoboron compounds. The goal is to develop new reactions that use these organoboron compounds to access common structures that are found in biologically active compounds.
|O'Neil, Gregory W; Cummins, Elizabeth J (2017) Iodine-mediated rearrangements of diallylsilanes. Tetrahedron Lett 58:3406-3409|