Masters of Mediation: MN(SiMe3)2 in Functionalization of C(sp3)−H Latent Nucleophiles

• Published in: Chemistry : a European journal Vol. 30; no. 29; pp. e202400435 - n/a
• Main Authors: Sreedharan, Ramdas, Gandhi, Thirumanavelan
• Format: Journal Article
• Language: English
• Published: Germany Wiley Subscription Services, Inc 23.05.2024
• Subjects: Alkali metals; C(sp3)−H bond functionalization; Catalysis; cation-π interaction; Chemical reactions; Chemical synthesis; Cross coupling; Hydrogen bonds; MN(SiMe3)2; Nucleophiles; Petrochemicals; Reagents; sustainability; cation-π interaction; C(sp3)−H bond functionalization; MN(SiMe3)2; Alkali metals; Sustainability
• ISSN: 0947-6539; 1521-3765; 1521-3765
• DOI: 10.1002/chem.202400435

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(sp3)−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(SiMe3)2 (M=Li, Na, K & Cs) reagent revived in C(sp3)−H bond functionalization over recent years in organic synthesis is showcased in this minireview. MN(SiMe3)2 reagent with higher reactivity, enhanced stability, and bespoke cation‐π interaction have shown eye‐opening mediated processes such as C(sp3)−C(sp3) 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(SiMe3)2 reagent in unreactive and robust C−X (X=O, N, F, C) bond cleavage reactions that occurred alongside the C(sp3)−H bond functionalization. Overall, this review encourages the community to exploit the untapped potential of MN(SiMe3)2 reagent and also inspires them to take up this subject to even greater heights. MN(SiMe3)2 mediated various functionalization of C(sp3)−H latent nucleophiles is summarized in this minireview. These alkali metal chemistries are competitive to the existing methodology, and performs unusual organic transformations, thus opening up new vistas in organic synthesis.