Arsenous chloride-free synthesis of cyclic tertiary organoarsines from arylarsine oxides and di-Grignard reagents

•Synthesis of Arsine Heterocycles.•Reagents are safe and are not chemical warfare reagents.•Unified strategy applicable to a range of arsine heterocycle types.•Repeatable, straightforward reactions giving reliable acceptable yields.

The growing importance of triarylarsines as ligands for transition metal catalysis has sparked recent interest in new synthetic routes to tertiary arsines that avoid hazardous arsenous chloride reagents. However, safer methods for the synthesis of lesser explored arsine heterocycles, especially those containing As–C(sp3) bonds, remain lacking. We demonstrate for the first time that bench stable, less hazardous, arylarsine(III) oxides are effective substitutes for their corresponding chlorides in the one-pot construction of cyclic tertiary organoarsines from di-Grignard reagents. Several known and novel heterocycles have been prepared in reasonable yields, accommodating variations in both the diorganomagnesium reagent and electrophile, making this a modular approach to cyclic arsine assembly.

Graphical abstractDemonstrated for the first time is stable, less hazardous, arylarsine(III) oxides are effective substitutes for the corresponding chlorides in one-pot constructions of cyclic tertiary organoarsines from di-Grignard reagents. Known and novel heterocycles were prepared, with variations in the diorganomagnesium reagent and electrophile; this a modular approach to cyclic arsine assembly.Figure optionsDownload full-size imageDownload as PowerPoint slide