Masters of Mediation: MN(SiMe) in Functionalization of C(sp)-H Latent Nucleophiles.

Chemistry

Department of Chemistry, School of Advanced Sciences, Vellore Institute of Technology, Vellore, 632014, Tamil Nadu, India.

Published: May 2024

Organoalkali compounds have undergone a far-reaching transformation being a coupling partner to a mediator in unusual organic conversions which finds its spot in the field of sustainable synthesis. Transition-metal catalysis has always been the priority in C(sp)-H bond functionalization, however alternatively, in recent times this has been seriously challenged by earth-abundant alkali metals and their complexes arriving at new sustainable organometallic reagents. In this line, the importance of MN(SiMe) (M=Li, Na, K & Cs) reagent revived in C(sp)-H bond functionalization over recent years in organic synthesis is showcased in this minireview. MN(SiMe) reagent with higher reactivity, enhanced stability, and bespoke cation-π interaction have shown eye-opening mediated processes such as C(sp)-C(sp) cross-coupling, radical-radical cross-coupling, aminobenzylation, annulation, aroylation, and other transformations to utilize readily available petrochemical feedstocks. This article also emphasizes the unusual reactivity of MN(SiMe) reagent in unreactive and robust C-X (X=O, N, F, C) bond cleavage reactions that occurred alongside the C(sp)-H bond functionalization. Overall, this review encourages the community to exploit the untapped potential of MN(SiMe) reagent and also inspires them to take up this subject to even greater heights.

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http://dx.doi.org/10.1002/chem.202400435DOI Listing

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