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Photochemical Strain‐Release‐Driven Cyclobutylation of C(sp 3 )‐Centered Radicals
Author(s) -
Ernouf Guillaume,
Chirkin Egor,
Rhyman Lydia,
Ramasami Ponnadurai,
Cintrat JeanChristophe
Publication year - 2020
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201908951
Subject(s) - cyclobutanes , radical , bicyclic molecule , chemistry , reactivity (psychology) , butane , olefin fiber , photoredox catalysis , photolyase , photochemistry , catalysis , medicinal chemistry , stereochemistry , organic chemistry , cycloaddition , photocatalysis , medicine , pathology , alternative medicine , biochemistry , dna repair , gene
A new photoredox‐catalyzed decarboxylative radical addition approach to functionalized cyclobutanes is described. The reaction involves an unprecedented formal Giese‐type addition of C(sp 3 )‐centered radicals to highly strained bicyclo[1.1.0]butanes. The mild photoredox conditions, which make use of a readily available and bench stable phenyl sulfonyl bicyclo[1.1.0]butane, proved to be amenable to a diverse range of α‐amino and α‐oxy carboxylic acids, providing a concise route to 1,3‐disubstituted cyclobutanes. Furthermore, kinetic studies and DFT calculations unveiled mechanistic details on bicyclo[1.1.0]butane reactivity relative to the corresponding olefin system.