Electronic control over site-selectivity in hydrogen atom transfer (HAT) based C(sp)-H functionalization promoted by electrophilic reagents

The direct functionalization of C(sp 3 )-H bonds represents one of the most investigated approaches to develop new synthetic methodology. Among the available strategies for intermolecular C-H bond functionalization, increasing attention has been devoted to hydrogen atom transfer (HAT) based procedur...

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Published inChemical Society reviews Vol. 51; no. 6; pp. 2171 - 2223
Main Authors Galeotti, Marco, Salamone, Michela, Bietti, Massimo
Format Journal Article
LanguageEnglish
Published England Royal Society of Chemistry 21.03.2022
Subjects
Electronic control
Electronics
Hydrogen - chemistry
Hydrogen atoms
Hydrogen Bonding
Hydrogen bonds
Indicators and Reagents
Organic chemistry
Radicals
Reagents
Selectivity
Substrates
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Summary:The direct functionalization of C(sp 3 )-H bonds represents one of the most investigated approaches to develop new synthetic methodology. Among the available strategies for intermolecular C-H bond functionalization, increasing attention has been devoted to hydrogen atom transfer (HAT) based procedures promoted by radical or radical-like reagents, that offer the opportunity to introduce a large variety of atoms and groups in place of hydrogen under mild conditions. Because of the large number of aliphatic C-H bonds displayed by organic molecules, in these processes control over site-selectivity represents a crucial issue, and the associated factors have been discussed. In this review article, attention will be devoted to the role of electronic effects on C(sp 3 )-H bond functionalization site-selectivity. Through an analysis of the recent literature, a detailed description of the HAT reagents employed in these processes, the associated mechanistic features and the selectivity patterns observed in the functionalization of substrates of increasing structural complexity will be provided. Leveraging on electronic effects in both the substrate and HAT reagent, site-selectivity can be implemented in C(sp 3 )-H bond functionalization.
Bibliography:3
Michela Salamone (left) is currently Associate Professor of Organic Chemistry at the University of Rome "Tor Vergata". Her scientific activity is mostly dedicated to the kinetic study of unimolecular and bimolecular reactions involving alkoxyl and aminoxyl radicals (fragmentation, rearrangement and atom transfer reactions) by means of time-resolved techniques, and to the use of this mechanistic information for the development of synthetically useful procedures. Massimo Bietti (centre) is Professor of Organic Chemistry at the University of Rome "Tor Vergata". His research activity is mainly focused on the study of the role of structural and medium effects on hydrogen atom transfer (HAT) reactions promoted by oxygen centered radical and radical-like species, aimed in particular at a deeper understanding of the factors that govern reactivity, site-selectivity and stereoselectivity in HAT-based C(sp
H bond functionalizations promoted by alkoxyl radicals, dioxiranes and metal-oxo species.
H bond functionalizations. Marco Galeotti (right) received his second level Degree in Chemistry in 2018 and is currently completing his PhD in Chemistry at the University of Rome "Tor Vergata" under the supervision of Massimo Bietti and Michela Salamone. His research activity has been mostly devoted toward the study of electronic, torsional and hyperconjugative effects in HAT-based C(sp
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ISSN:0306-0012
1460-4744
DOI:10.1039/d1cs00556a