Shamsabadi, André; (2020) Exploiting Aerobic C–H Bond Activation and the Synthetic Utility of Acyl Hydrazides. Doctoral thesis (Ph.D), UCL (University College London).

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Abstract

This project is focused on two separate but correlated fields of research. The first segment describes chemical transformations that are initiated by the reaction of organic species with dioxygen in air as means to construct C–N bonds via radical addition. The second segment explores the untapped synthetic utility of acyl hydrazides in order to form further desirable moieties. Chapter 1 introduces important fundamental ideas central to the project and covers the background for the structure, generation and behaviour of radical entities and modern methods for C–H bond functionalisation reactions. Furthermore, the reaction behaviour of azodicarboxylate and acyl hydrazide moieties are explored. Chapter 2 describes C–H amination of ethereal compounds using azodicarboxylates as the nitrogen source and fluorinated alcohols as the reaction solvent. Reaction optimisation and mechanistic evaluation through NMR titration and theoretical analysis are discussed. Chapter 3 details the use of acyl hydrazides, obtained from aerobic-based hydroacylation of azodicarboxylates in high yields, in a one-pot synthesis of N-acyl carbamates. Reaction optimisation and substrate scope are covered. Chapter 4 reports a direct transformation of acyl hydrazides into 2-hydrazobenzophenones via a molecular rearrangement involving an aryne intermediate. The mechanism of the transformation is studied and evaluated. Furthermore, the corresponding products are amenable to further derivatisation to afford both 1H- and 2H-indazoles.

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