Chemistry of Four-Membered Ring Compounds Containing a Hypervalent Sulfur Atom and a Heteroatom at the Neighbor Positions

Abstract

Title compounds containing tetracoordinated and pentacoordinated sulfur together with oxygen, nitrogen, or sulfur were successfully synthesized as stable compounds. They contain the Martin ligand, which is well known to be able to stabilize such highly coordinated main group compounds. X-ray crystallographic analyses revealed that they have distorted trigonal bipyramidal (TBP) or pseudo-TBP structures. In marked contrast to group 13-15 element analogues, which afford the corresponding alkenes upon heating, thermolyses of compounds bearing an oxygen or nitrogen atom gave the corresponding oxiranes or aziridine, suggesting the possibility that these compounds are intermediates of the Corey-Chaykovsky reaction of sulfur ylides with carbonyl compounds or imines. Thermolysis of 1λ 4 ,2-dithietanes also gave the corresponding thiiranes. The stereochemistry (retention of configuration) of formation of these three-membered ring compounds is also described.

Organohypervalent heterocycles

“…19). 202 In particular, this group synthesized tetracoordinated and pentacoordinated 1,2-oxathietanes 93 and 94, as shown in Scheme 15, and reported their thermolysis. These compounds having a tetracoordinated or pentacoordinated hypervalent sulfur atom collectively with other heteroatoms were isolated as thermally stable products and structurally characterized through single-crystal XRD.…”