Studies towards Enantioselective Silver-Catalysed C-H Amination via Nitrene Transfer using Multi-Functional Ligands

Lead Research Organisation: University of Cambridge
Department Name: Chemistry

Abstract

Year 1: Generic training activities for all first-year student members of the CDT.

Year 2-4: C-H amination via nitrene transfer (NT) is able to convert C-H bonds directly to C-N bonds and holds the potential to transform the synthesis of nitrogen-containing molecules. NT reactions have gained much interest in the last 25 years as an alternative to cross-coupling reactions. Whilst chemo- and site-selectivity in C-H amination reactions is now well established, enantioselectivity is still a challenge. It is often the case that elaborate chiral ligands are required to see any enantioinduction for a given substrate class. Recently, silver has gained interest for its wide range of coordination geometries and ability to host non-covalent interactions (NCIs) between reactants and ligands. Enantioselective silver-catalysed C-H amination via NT has been seldom explored with only a handful of examples successfully developed thus far.

Our group has successfully shown that enantioselectivity in C-H borylation can be controlled by a chiral-cation that is associated with an achiral, anionic ligand for iridium. With the potential for this methodology to be broadly applied to a range of other transition metal (TM) catalysed reactions, the ion-paired ligand system will be investigated with a silver-catalysed C-H amination protocol.

Publications

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Studentship Projects

Project Reference Relationship Related To Start End Student Name
EP/S024220/1 31/05/2019 30/11/2027
2468366 Studentship EP/S024220/1 30/09/2020 29/09/2024 Hannah Adams