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

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Catalysis for Clean Energy and Environmental Sustainability

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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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Acknowledgments

The authors thank CSIR (CSMCRI project no. MLP 0028) and DST (Grant no. DST/INSPIRE/04/2015/002248) for financial support. CSIR-CSMCRI Communication no. 10/2020.

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Authors and Affiliations

  1. Inorganic Materials and Catalysis Division, Academy of Scientific and Innovative Research (AcSIR), Ghaziabad, India

    Aniket Gupta, Sreedhar Gundekari & Sukalyan Bhadra

  2. CSIR-Central Salt and Marine Chemicals Research Institute, Bhavnagar, Gujarat, India

    Aniket Gupta, Sreedhar Gundekari & Sukalyan Bhadra

Authors
  1. Aniket Gupta
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  2. Sreedhar Gundekari
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  3. Sukalyan Bhadra
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Correspondence to Sukalyan Bhadra .

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Editors and Affiliations

  1. Department of Chemical Engineering, Indian Institute of Technology Delhi, New Delhi, Delhi, India

    K. K. Pant

  2. Department of Civil Engineering, Indian Institute of Technology Delhi, New Delhi, Delhi, India

    Sanjay Kumar Gupta

  3. Department of Chemical Engineering, Indian Institute of Technology (ISM) Dhanbad, Dhanbad, Jharkhand, India

    Ejaz Ahmad

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Gupta, A., Gundekari, S., Bhadra, S. (2021). C(sp3)–H Bond Hetero-functionalization of Aliphatic Carboxylic Acid Equivalents Enabled by Transition Metals. In: Pant, K.K., Gupta, S.K., Ahmad, E. (eds) Catalysis for Clean Energy and Environmental Sustainability. Springer, Cham. https://doi.org/10.1007/978-3-030-65017-9_13

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