Fluorine compounds are known for their abundance in more than 20% of pharmaceutical and agrochemical products mainly due to the enhanced lipophilicity, metabolic stability and pharmacokinetic properties of organofluorides. Consequently,...
Transition metal mediated C-H functionalizations have been a relevant realm in organic synthesis for decades. However, sustainability as an inherent feature in such transformations remains under-explored. Through a varied palate,...
Supported metal nanoparticles (NPs) catalysed chemical transformations have been a vital area of research over the last few decades. Catalysis by supported NPs not only plays a pivotal role in the production of fine chemicals such as coupling products, heterocycles, alcohols, carbonyl compounds, acids, etc. but also provides sustainable chemical processes. The use of supported metal NPs provides a much prosperous basis than conventional homogeneous and heterogeneous catalysts for tuning reactivity, recyclability, high productivity and environment benevolent alternative for C−H functionalization. Consequently, as evidenced in the literature, various support materials such as silica, metal oxides, zeolites, carbon‐based materials, bio‐materials, magnetic materials, and MOFs have been moderately investigated in order to exploit their benefit in supported metal NPs catalyzed various C−H functionalizations. This review aims to summarize recent advances in the development of new support materials or novel supported NPs catalytic systems for functionalization of the challenging C−H bond under heterogeneous conditions. Furthermore, a deep scientific understanding of the mechanisms, active species, role of base and oxidants for these systems are also discussed to gain insight into the advance in the rational design of efficient catalytic systems, which may serve as an inspiration to researchers in their future work.
Allyl alcohols represent a unique class of coupling partners
in
C–H functionalization reactions. In this work, we report a
simple strategy that involves dual-1,1-C(sp3)–H
activation of free aliphatic acids, leading to the direct synthesis
of γ-lactones that contain α,β-unsaturated groups
at the γ-position. Various allyl alcohols including primary,
secondary, tertiary, etc., have been used as suitable coupling partners
to generate a diverse range of γ-lactones. A number of aliphatic
acids including the long-chain ones have been used as substrates in
the protocol. A mechanistic investigation has been carried out and
suggests C–H activation to be the rate-determining step and
a subsequent allylic C–H activation in the reaction. The synthesized
lactones having α,β-unsaturated fragments attached are
expected to be useful in the synthesis of complex molecules via further
synthetic manipulation.
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