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2021 | OriginalPaper | Buchkapitel

C(sp³)–H Bond Hetero-functionalization of Aliphatic Carboxylic Acid Equivalents Enabled by Transition Metals

verfasst von : Aniket Gupta, Sreedhar Gundekari, Sukalyan Bhadra

Erschienen in: Catalysis for Clean Energy and Environmental Sustainability

Verlag: Springer International Publishing

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Abstract

Aliphatic carboxylic acids and their common derivatives such as amides and esters, particularly embracing heteroatom-based substituents, are widespread among natural and synthetic complex molecular frameworks, ratified drugs, and various tailored materials. Conventional synthetic processes to access these compounds comprise multistep protocols that are virtually inconvenient and unsafe, generating large mass of wastes within the synthetic sequence. The straightforward transition metal-catalyzed installation of a heteroatom-based function via transforming a selective C–H bond of an aliphatic carboxylic acid equivalent has recently materialized as an attractive substitute to those multistep processes. In the latter case, the carboxylate group, either directly or in the form of an interconvertible directing group, controls the highly selective metal-promoted hetero-functionalization process in the alkyl chain residue through extraordinarily ordered transition states.

The current chapter summarizes the advances in the field of transition metal-enabled C(sp³)–H bond hetero-functionalization of aliphatic carboxylic acids and their synthetic equivalents. Due to substantial progress in recent years, only frequently employed transition metals, including palladium, nickel, copper, iron, and cobalt, which promoted reactions have been described. The chapter has been divided into two key subtopics: (1) directed C(sp³)–H hetero-functionalization approaches, in which the carboxylic acid or a promptly adaptable carboxylate equivalent actively binds to the metal catalyst and brings it close to the cleavable C(sp³)–H bond to facilitate further functionalization, and (2) non-directed C(sp³)–H hetero-functionalization approaches, in which the carboxylic acid equivalents passively control the metal-promoted C(sp³)–H functionalization. Gratifyingly, both approaches lead to regiospecific functionalization of carboxylic acid synthons at either proximal-selective α-C–H bonds or distal β-, γ-, and even δ-C–H bonds with various heteroatom-based substituents, e.g., O-, N-, S-, Se-, halogen-, B-, Si-, and recently Ge-based groups.

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Titel: C(sp3)–H Bond Hetero-functionalization of Aliphatic Carboxylic Acid Equivalents Enabled by Transition Metals
verfasst von: Aniket Gupta
Sreedhar Gundekari
Sukalyan Bhadra
Verlag: Springer International Publishing
Buch: Catalysis for Clean Energy and Environmental Sustainability
Print ISBN: 978-3-030-65016-2

Electronic ISBN: 978-3-030-65017-9

Copyright-Jahr: 2021
DOI: https://doi.org/10.1007/978-3-030-65017-9_13