Generation and reversible cyclisation of furfurylic radicals

Journal article

Abstract:: The chemistry of free radical intermediates has undergone a renaissance with the recent advent of alternatives to toxic, stoichiometric reagent systems and thermal reaction conditions. In this context, we describe an attempt to effect an isomerisation reaction comprising overall 5-exo-trig radical cyclisation preceded and followed by electron and proton transfer steps. In a follow-up study the 5-exo-trig cyclisation of furfurylic radicals, generated unambiguously by classical methods, is here shown to be synthetically viable, reversible, and equally effective with either an electron-deficient or an electron-rich alkene component. The experimental results are compared with DFT transition state and ground state energy calculations.

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Institution:: University of Oxford
Division:: MPLS
Department:: Chemistry
Sub department:: Organic Chemistry
Oxford college:: Brasenose College; Brasenose College; Brasenose College; Brasenose College;Brasenose College;Brasenose College;Brasenose College;Brasenose College;Brasenose College;Brasenose College
Role:: Author
ORCID:: 0000-0002-6809-8265

Language:: English
Keywords:: FFR

electron transfer catalysis

radical cyclisation

cyclopentanes

DFT calculations

furan α-radicals
Pubs id:: 1544318
Local pid:: pubs:1544318
Deposit date:: 2023-10-10

Copyright holder:: Lewis et al
Rights statement:: ©2023 The Authors. This paper is an open access article distributed under the terms of the Creative Commons Attribution (CC BY) license (http://creativecommons.org/licenses/by/4.0/)

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