Base-Mediated Direct C–H Germylation of Heteroarenes and Arenes

Abstract

The direct C−H germylation of heteroarenes, arenes, and benzylic C−H bonds promoted by lithium tetramethylpiperidide (LiTMP) is reported. The method is rapid, selective, and operationally simple, consisting of direct addition of all reagents at room temperature (one-pot procedure). The synthetic utility of these newly accessed aryl germanes as viable coupling partners in Pd catalysis is also showcased.

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

“…13 C­{ 1 H} NMR (101 MHz, CDCl 3 ) δ: 141.9, 128.2, 127.8, 123.7, 21.0, 8.9, 3.8 ppm. The spectroscopic data for this product match the literature …”

Base‐Mediated Radio‐Iodination of Arenes by Using Organosilane and Organogermane as Radiolabelling Precursors

“…More importantly, when applied to molecular tracers, the basemediated iodo-degermylation is a reliable tool, able to provide both the UV standard and the radio-iodinated scaffold with high radiochemical yield and molar activity. Combined with the low toxicity of arylgermanes and their straightforward access, from metalation, palladium catalyzed-or photoredox mediatedgermylation, [64][65][66][67][68][69][70] we anticipate that the base-mediated radioiododegermylation has the potential to be an alternative to radio-iododestannylation under clinical applications.…”

Recent Developments with Organogermanes: their Preparation and Application in Synthesis and Catalysis

“…[12] As an extension of this methodology, in 2021 we also coupled vinyl-and heteroaryl organogermanes with aryl halides utilizing the Pd-nanoparticlecatalyzed conditions. [14] After unlocking an orthogonal method for activating the ArGeEt 3 reagent via an electrophilic Pd-based species, we then explored alternative transition-metal electrophiles that could engage the trialkylgermane À C sp 2 cross couplings with aryl germatranes. [10] B) Recent use of modified germatrane structures for (hetero)aryl coupling with (pseudo)halides.…”