Theoretical Examination of the S–C–P Anomeric Effect
The Journal of Organic Chemistry2015Vol. 80(5), pp. 2879–2883
Citations Over TimeTop 14% of 2015 papers
Abstract
Three decades after the discovery of a strong S-C-P anomeric effect in 2-diphenylphosphinoyl-1,3-dithiane (1) and 2-trimethylphosphonium-1,3-dithiane (4), its definitive interpretation is still lacking. The present study reports DFT geometry optimizations of 1-ax, 1-eq, 4-ax, and 4-eq, which do reproduce the S-C-P anomeric effect in 1 and 4, worth 5.45 and 3.08 kcal/mol, respectively (in chloroform solvent). Weinhold's NBO analysis supports the existence of dominant nX → σ*C-Y stereoelectronic interactions that stabilize the axial conformers.
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