Developing a Catalytic Strategy to Address Regiocontrol in Radical Reactions of Aromatic Heterocycles
Lead Research Organisation:
University of Cambridge
Department Name: Chemistry
Abstract
Construction of basic heteroarenes with varied substitution patterns is of great importance, but direct transformation of heterocyclic C-H bonds is a major challenge, often due to incompatibility with metal catalysts. Minisci-type additions are radical addition processes in which a basic heterocycle is protonated with a concomitant lowering of its LUMO, before attack by 'nucleophilic' radicals. This is a deceptively simple method with no catalyst required. The problem that has held back its widespread use is a lack of regioselectivity on heterocycles such as pyridines and quinolines due to insufficiently different LUMO coefficients of the C2 and C4 positions. We will develop a catalytic approach to Minisci additions that will allow us to control regioselectivity between C2 and C4. We anticipate that successful realisation of this strategy will allow the wealth of radical chemistry to be applied to valuable basic heterocycles with new-found regiocontrol.
Publications
Colgan AC
(2022)
Hydrogen Atom Transfer Driven Enantioselective Minisci Reaction of Alcohols.
in Angewandte Chemie (International ed. in English)
Proctor R
(2019)
Recent Advances in Minisci-Type Reactions
in Angewandte Chemie International Edition
Proctor R
(2018)
Catalytic enantioselective Minisci-type addition to heteroarenes.
Proctor R
(2019)
Recent Advances in Minisci-Type Reactions.
Proctor R
(2020)
Development of Catalytic Enantioselective Minisci-type Reactions
Proctor RSJ
(2018)
Catalytic enantioselective Minisci-type addition to heteroarenes.
in Science (New York, N.Y.)
Studentship Projects
Project Reference | Relationship | Related To | Start | End | Student Name |
---|---|---|---|---|---|
EP/N509620/1 | 30/09/2016 | 29/09/2022 | |||
1918560 | Studentship | EP/N509620/1 | 30/09/2016 | 29/09/2020 | Rupert Proctor |