Radical hydroacylation of C-C and N-N double bonds in air

摘要

The formation of C-C and C-N bonds in modern organic synthesis is a key target forudmethodological advancement. Current methods of C-C and C-N bond formationudoften involve the use of expensive catalysts, or sub-stoichiometric reagents, whichudcan lead to the generation of undesirable waste products. This thesis describes audnovel and environmentally benign set of reaction conditions for the formation of C-Cudand C-N bonds by hydroacylation and this is promoted by mixing two reagents, anudaldehyde and an electron-deficient double bond, under freely available atmosphericudoxygen at room temperatureudChapter 1 will provide an introduction to the thesis and mainly discusses methods forudC-C bond formation, in particular, radical chemistry and hydroacylation. Chapter 2uddescribes the hydroacylation of vinyl sulfonates and vinyl sulfones (C-C doubleudbonds) with aliphatic and aromatic aldehydes with a discussion and evidence for theudmechanism of the transformation. Chapter 3 details the synthesis of precursors forudintramolecular cyclisations and studies into aerobic intramolecular cyclisations.udChapter 4 describes the hydroacylation of vinyl phosphonates (C-C double bonds)udand diazocarboxylates (N-N double bonds) with aliphatic and aromatic aldehydesudbearing functional groups. In addition, the hydroacylation of diazocarboxylates withudchiral aldehydes will be discussed.udIn conclusion, a new, facile and clean set of reaction conditions for the formation ofudC-C and C-N bonds has been developed via aerobic C-H activation of aldehydesudproviding access to unsymmetrical ketones.