Transition metal-catalyzed C-C/C-N bond formation

Abstract

Imide derivatives are widely used organic compounds. To address the challenge of atom-economical synthesis of imide derivatives, chapter 1 describes the first synthesis of cyclic imides from linear diols and amines using a NHC-based ruthenium catalyst with the liberation of hydrogen. In chapter 2, the dehydrogenation methodology is expanded to direct N-acylation of lactams, oxazolidinones, and imidazolidinones with aldehydes using Shvo’s catalyst, a cyclopentadienone-ligated ruthenium complex. 1,3-Butadiene is an important structural motif in organic chemistry. Chapter 3 describes ruthenium- and rhodium-catalyzed direct cross-coupling reaction between acrylamides and electron-deficient alkenes to produce (Z,E)-dienamides in high efficiency. Both of two catalytic systems allowed oxidative olefination of a wide range of alkenes bearing different functional groups, such as CO2R, SO2Ph, aryl, CONHBn, CN, PO(OEt)2, as well as Weinreb amide. With the possible depletion of fossil fuels in near future, many efforts have been made to convert lignin to useful platform chemicals.The most abundant unit of lignin is the β-O-4 linkage. Chapter 4 describes simple and efficient methods for conversion of the lignin β-O-4 models into amide derivatives and phenols. The conversion is achieved via chemo-selective oxidation of the secondary benzylic alcohol and subsequent Cu-catalyzed aerobic amide bond formation. Imidazo[1,2-a]pyridine is an important structural moiety appearing in pharmacologically important molecules. Chapter 5 describes a method for the aerobic oxidative synthesis of imidazo[1,2-a]pyridines from aryloxyacetophenone and 2-aminopyridines by copper catalyst.