Hydrogen Atom Transfer Driven Enantioselective Minisci Reaction of Alcohols
Authors
Colgan, Avene C
Proctor, Rupert SJ
Gibson, David C
Chuentragool, Padon
Lahdenperä, Antti SK
Phipps, Robert J
Publication Date
2022-04-27Journal Title
Angewandte Chemie
ISSN
0044-8249
Language
en
Type
Article
This Version
AO
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Colgan, A. C., Proctor, R. S., Gibson, D. C., Chuentragool, P., Lahdenperä, A. S., Ermanis, K., & Phipps, R. J. (2022). Hydrogen Atom Transfer Driven Enantioselective Minisci Reaction of Alcohols. Angewandte Chemie https://doi.org/10.1002/ange.202200266
Abstract
Abstract: Catalytic enantioselective Minisci reactions have recently been developed but all instances so far utilize α‐amino radical coupling partners. We report a substantial evolution of the enantioselective Minisci reaction that enables α‐hydroxy radicals to be used, providing valuable enantioenriched secondary alcohol products. This is achieved through the direct oxidative coupling of two C−H bonds on simple alcohol and pyridine partners through a hydrogen atom transfer (HAT)‐driven approach: a challenging process to achieve due to the numerous side reactions that can occur. Our approach is highly regioselective as well as highly enantioselective. Dicumyl peroxide, upon irradiation with 390 nm light, serves as both HAT reagent and oxidant whilst selectivity is controlled by use of a chiral phosphoric acid catalyst. Computational and experimental evidence provide mechanistic insight as to the origin of selectivity, revealing a stereodetermining deprotonation step distinct from the analogous reaction of amide‐containing substrates.
Keywords
Forschungsartikel, Asymmetric Catalysis, Chiral Phosphoric Acids, Heterocycles, Minisci Reaction, Organocatalysis
Sponsorship
Horizon 2020 (757381)
Engineering and Physical Sciences Research Council (EP/S03269X/1, EP/P020259/1)
EPSRC and Syngenta (PhD Studentship)
The Royal Society (URF)
EPSRC and GSK (Case Studentship)
Leverhulme Trust (ECF-2017-255)
Isaac Newton Trust (17.08(d))
Identifiers
ange202200266
External DOI: https://doi.org/10.1002/ange.202200266
This record's URL: https://www.repository.cam.ac.uk/handle/1810/336541
Rights
Licence:
http://creativecommons.org/licenses/by/4.0/
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