7205-77-8Relevant academic research and scientific papers
Thermolysis-Induced Two- or Multicomponent Tandem Reactions Involving Isocyanides and Sulfenic-Acid-Generating Sulfoxides: Access to Diverse Sulfur-Containing Functional Scaffolds
Wu, Shengfeng,Lei, Xiaofang,Fan, Erkang,Sun, Zhihua
, p. 522 - 525 (2018/02/10)
Direct reaction of isocyanides with some sulfenic-acid-generating sulfoxides led to the effective formation of the corresponding thiocarbamic acid S-esters in good to high yields. A multicomponent reaction involving isocyanide, sulfoxide, and a suitable nucleophile has also been developed, providing ready access to a diverse range of sulfur-containing compounds, including isothioureas, carbonimidothioic acid esters, and carboximidothioic acid esters.
A kinetic investigation, supported by theoretical calculations, of steric and ring strain effects on the oxidation of sulfides and sulfoxides by dimethyldioxirane in acetone
Hanson, Peter,Hendrickx, Ramon A. A. J.,Lindsay Smith, John R.
scheme or table, p. 65 - 84 (2011/01/07)
The oxidations of alkyl 4-nitrophenyl, and dialkyl, sulfides and sulfoxides by dimethyldioxirane in acetone occur by concerted mechanisms but the sulfides respond differently from the sulfoxides to variation in the alkyl group. The reactions of the sulfides are inhibited by the steric effects of alkyl groups and these predominate over their inductive effects. By contrast, the reactions of these limited sets of sulfoxides are insensitive to alkyl steric effects but there is an indication of steric acceleration when a broader set of sulfoxides is considered. This behaviour is rationalised in terms of the differences in dipolar charge and its solvation between the ground state and transition state for the two types of substrate. The oxidations of cyclic sulfides and sulfoxides also exhibit contrasting behaviour. The reactivity of the sulfides is insensitive to ring strain but is explicable in frontier orbital terms whereas that of the sulfoxides is partly dependent upon the change in ring strain between reactant and product on oxidation, a difference rationalised in terms of the relative positions of the transition states in the reaction coordinates of the two oxidations. The reactivity of 4-, 5- and 6-membered cyclic sulfoxides is also dependent on a ring-size related property of the transition state. Calculations at the B3-LYP/6-31G* level of density functional theory on both ground states and transition states, including simulation of solvation by acetone, strongly support the mechanistic conclusions reached in this and earlier work.
