One-Pot Rapid Access to Benzyl Silanes, Germanes, and Stannanes from Toluenes Mediated by a LiN(SiMe₃)₂/CsCl System

Abstract

Organo-silanes, germanes, and stannanes are considered to be conducive to the development of cross-coupling reactions because they are stable, nontoxic, and easy to handle. Using feedstock toluenes, one-pot direct benzylic C–H silylations, germylations, and stannylations are developed. Simply combining toluenes, LiN(SiMe3)2/CsCl, and R3MCl (M = Si, Ge, Sn) generates a diverse array of bench-stable benzyl silanes, germanes, and stannanes (38 examples, 53–90% yields). The syntheses developed here are easy to access on scale.

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

“…As such, tremendous effort has been devoted to their synthesis, in 2022 Mao elegantly disclosed the synthesis of bench stable benzyl silanes 101 a , germanes 101 b and d and stannanes 101 c using abundant petrochemical feedstock toluene and their derivatives in one‐pot manner by employing LiN(SiMe 3 ) 2 /CsCl system (Scheme 43). [110] The reported method is scalable and further applied to other functionalization such as arylation to yield highly functionalized silanes and germanes. In addition, it is evaluated to carboxylation and condensation in delivering carboxylic acids and stilbenes respectively.…”

Synthesis of Alkynylsilanes: A Review of the State of the Art

“…Additionally, there has been a recent surge in published articles discussing the use of LiN(SiMe 3 ) 2 as a deprotonating reagent. [70][71][72][73][74] Moreover, the reactions described by Chen proceed under mild conditions, at room temperature for 15 hours.…”

Alkali–Amide-Catalyzed One-Pot Aminoallylation of Aldehydes with Allylbenzenes

“…So far, several tandem transformations were developed as follows: (1) NaN­(SiMe 3 ) 2 /CsTFA mediated one-pot aminobenzylations of aldehyde with toluene (Scheme a); (2) LiN­(SiMe 3 ) 2 /CsF-facilitated chemoselective deprotonation of 2-fluorotoluene to build indoles (Scheme b); (3) LiN­(SiMe 3 ) 2 /CsF-mediated one-pot benzylic aroylation of toluenes; and many others . These successful one-pot transformations inspired us to wonder if allylbenzene could be chemoselectively deprotonated and trapped with our in situ generated imines.…”