10413-63-5Relevant academic research and scientific papers
Decatungstate-Catalyzed C(sp3)-H Sulfinylation: Rapid Access to Diverse Organosulfur Functionality
Bissonnette, Noah B.,Macmillan, David W. C.,Sarver, Patrick J.
, p. 9737 - 9743 (2021/07/19)
Here we report the direct conversion of strong, aliphatic C(sp3)-H bonds into the corresponding alkyl sulfinic acids via decatungstate photocatalysis. This transformation has been applied to a diverse range of C(sp3)-rich scaffolds, including natural products and approved pharmaceuticals, providing efficient access to complex sulfur-containing products. To demonstrate the broad potential of this methodology for the divergent synthesis of pharmaceutically relevant molecules, procedures for the diversification of the sulfinic acid products into a range of medicinally relevant functional groups have been developed.
Investigation of steric and electronic effects in the copper-catalysed asymmetric oxidation of sulfides
O'Mahony, Graham E.,Eccles, Kevin S.,Morrison, Robin E.,Ford, Alan,Lawrence, Simon E.,Maguire, Anita R.
, p. 10168 - 10184 (2013/11/06)
Steric and electronic effects in the copper-catalysed asymmetric oxidation of aryl benzyl, aryl alkyl and alkyl benzyl sulfides have been investigated. The presence of an aryl group directly attached to the sulfur is essential to afford sulfoxides with high enantioselectivities, with up to 97% ee for 2-naphthyl benzyl sulfoxide, the highest enantioselectivity achieved to date for copper-catalysed asymmetric sulfoxidation. In contrast, the benzyl substituent can be replaced by sterically comparable groups with no effect on enantioselectivity. Copper-mediated oxidation of substituted aryl benzyl sulfides display modest steric and electronic effects resulting in comparable or lower enantioselectivities to those obtained with the unsubstituted benzyl phenyl sulfide.
Synthesis of novel sulfonyl-stabilized phosphorus ylides, and the kinetics and mechanism of their conventional and flash vacuum pyrolysis reactions
Al-Bashir, Rasha F.,Al-Awadi, Nouria A.,El-Dusouqui, Osman M.E.
, p. 1543 - 1553 (2007/10/03)
Nine substituted sulfonyl-stabilized phosphorus ylides were prepared by treating their intermediate ylide analogues with phenylmethanesulfonyl fluoride. The stoichiometric ratio of the reactants for each preparation needed to be adjusted according to the basicity of each ylide intermediate. The nine ylide compounds were then subjected to conventional (sealed-tube) gas-phase pyrolysis at 470-545 K. The pyrolytic reactions were homogeneous and obeyed a first-order rate equation. The values of the Arrhenius log A (s-1) and E a (kJ mol-1) obtained for these reactions averaged 11.12 ± 2.00 and 131.8 ± 24.4, respectively. Analysis of the pyrolysates from conventional pyrolysis and from flash vacuum pyrolysis at 600 K showed the products to be complex mixtures of triphenylphosphine, triphenylphosphine oxide, triphenylphosphine sulfide, and symmetric and unsymmetric alkenes. Conventional pyrolysis also gave novel mixed sulfones and, for the p-methoxyaryl substituent, p-anisaldehyde. The products of the reactions under study are explained on the basis of a mechanism involving a sulfonyl carbene intermediate, and the reaction mechanism is used to rationalize the kinetic results and molecular reactivities.
