4184-40-1Relevant articles and documents
Chromoselective Synthesis of Sulfonyl Chlorides and Sulfonamides with Potassium Poly(heptazine imide) Photocatalyst
Antonietti, Markus,Guldi, Dirk M.,Markushyna, Yevheniia,Savateev, Aleksandr,Schü?lbauer, Christoph M.,Ullrich, Tobias
, p. 20543 - 20550 (2021)
Among external stimuli used to promote a chemical reaction, photocatalysis possesses a unique one—light. Photons are traceless reagents that provide an exclusive opportunity to alter chemoselectivity of the photocatalytic reaction varying the color of incident light. This strategy may be implemented by using a sensitizer capable to activate a specific reaction pathway depending on the excitation light. Herein, we use potassium poly(heptazine imide) (K-PHI), a type of carbon nitride, to generate selectively three different products from S-arylthioacetates simply varying the excitation light and otherwise identical conditions. Namely, arylchlorides are produced under UV/purple, sulfonyl chlorides with blue/white, and diaryldisulfides at green to red light. A combination of the negatively charged polyanion, highly positive potential of the valence band, presence of intraband states, ability to sensitize singlet oxygen, and multi-electron transfer is shown to enable this chromoselective conversion of thioacetates.
Dynamic kinetic resolution of allylic sulfoxides by Rh-catalyzed hydrogenation: A combined theoretical and experimental mechanistic study
Dornan, Peter K.,Kou, Kevin G. M.,Houk,Dong, Vy M.
supporting information, p. 291 - 298 (2014/01/23)
A dynamic kinetic resolution (DKR) of allylic sulfoxides has been demonstrated by combining the Mislow [2,3]-sigmatropic rearrangement with catalytic asymmetric hydrogenation. The efficiency of our DKR was optimized by using low pressures of hydrogen gas to decrease the rate of hydrogenation relative to the rate of sigmatropic rearrangement. Kinetic studies reveal that the rhodium complex acts as a dual-role catalyst and accelerates the substrate racemization while catalyzing olefin hydrogenation. Scrambling experiments and theoretical modeling support a novel mode of sulfoxide racemization which occurs via a rhodium π-allyl intermediate in polar solvents. In nonpolar solvents, however, the substrate racemization is primarily uncatalyzed. Computational studies suggest that the sulfoxide binds to rhodium via O-coordination throughout the catalytic cycle for hydrogenation.
Simple, extremely fast, and high-yielding oxidation of thiols to disulfides
Alam, Ashraful,Takaguchi, Yutaka,Tsuboi, Sadao
, p. 1329 - 1333 (2007/10/03)
Results of oxidation of thiols to disulfides with 1,3-dibromo-5,5-dimethyl- hydantoin (DBDMH) are described. A simple addition of 0.20-0.25 mol equivalent of solid DBDMH to thiol in chloroform at room temperature yielded the disulfides in excellent yield. The reaction is extremely fast and gave no other oxidized side products. Copyright Taylor & Francis, Inc.
