Carbon-Nitrogen Bond Formation Using Sodium Hexamethyldisilazide: Solvent-Dependent Reactivities and Mechanisms.

ABSTRACT: The solvent-dependent reactivity of sodium hexamethyldisilazide (NaHMDS) toward carbon-centered electrophiles reveals reactions that are poorly represented or unrepresented in the literature, including direct aminolysis of aromatic methyl esters to give carboxamides, nitriles, or amidines, depending on the choice of solvent. S_NAr substitutions of aryl halides and opening of terminal epoxides are also examined. A combination of ¹H and ²⁹Si nuclear magnetic resonance (NMR) spectroscopic studies using [¹⁵N]NaHMDS, kinetic studies, and computational studies reveals the complex mechanistic basis of the preferences for simple aryl carboxamides in toluene and dimethylethylamine and arylnitriles or amidines in tetrahydrofuran (THF). A prevalence of dimer

SUBMITTER: You Q 

PROVIDER: S-EPMC11373886 | biostudies-literature | 2023 Nov

REPOSITORIES: biostudies-literature