Selective functionalization of unactivated aliphatic C-H bonds represents an important goal of modern synthetic chemistry. Differentiating between such bonds in organic molecules with high levels of selectivity remains a crucial issue, and a profound understanding of even the subtlest reactivity trends is needed. Among the methodologies that have been developed, those based on hydrogen atom transfer (HAT) have attracted considerable interest. Within this framework, medium effects have proved effective in altering the reactivity and site-selectivity in synthetically useful C-H functionalization procedures. In this Review, the mechanistic features behind the available strategies are discussed. It is shown that hydrogen bonding and acid-base interactions can promote C-H bond activation or deactivation toward HAT reagents, thereby providing fine control over the site-selectivity and product chemoselectivity as well as useful guidelines for future development and applications.

Bietti, M. (2018). Activation and Deactivation Strategies Promoted by Medium Effects for Selective Aliphatic C-H Bond Functionalization. ANGEWANDTE CHEMIE. INTERNATIONAL EDITION, 57, 16618-16637 [10.1002/anie.201804929].

Activation and Deactivation Strategies Promoted by Medium Effects for Selective Aliphatic C-H Bond Functionalization

Massimo Bietti
2018-11-08

Abstract

Selective functionalization of unactivated aliphatic C-H bonds represents an important goal of modern synthetic chemistry. Differentiating between such bonds in organic molecules with high levels of selectivity remains a crucial issue, and a profound understanding of even the subtlest reactivity trends is needed. Among the methodologies that have been developed, those based on hydrogen atom transfer (HAT) have attracted considerable interest. Within this framework, medium effects have proved effective in altering the reactivity and site-selectivity in synthetically useful C-H functionalization procedures. In this Review, the mechanistic features behind the available strategies are discussed. It is shown that hydrogen bonding and acid-base interactions can promote C-H bond activation or deactivation toward HAT reagents, thereby providing fine control over the site-selectivity and product chemoselectivity as well as useful guidelines for future development and applications.
8-nov-2018
Pubblicato
Rilevanza internazionale
Articolo
Esperti anonimi
Settore CHIM/06 - CHIMICA ORGANICA
English
Con Impact Factor ISI
acid-base interactions; C-H activation; hydrogen atom transfer; hydrogen bonding; oxidation
Bietti, M. (2018). Activation and Deactivation Strategies Promoted by Medium Effects for Selective Aliphatic C-H Bond Functionalization. ANGEWANDTE CHEMIE. INTERNATIONAL EDITION, 57, 16618-16637 [10.1002/anie.201804929].
Bietti, M
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/2108/232172
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