19294-29-2Relevant academic research and scientific papers
A new preparative method of thiocanates by the solid state thiosulfonate/cyanide reaction
Fujiki, Kiyoko,Yoshida, Eiji
, p. 3289 - 3294 (1999)
The mixing and heating of thiosulfonates with potassium cyanide in the solid state gave a variety of thiocyanates in good yield. This method provides easy access to aryl thiocyanates.
Mechanistic Studies of the Palladium-Catalyzed Desulfinative Cross-Coupling of Aryl Bromides and (Hetero)Aryl Sulfinate Salts
Davis, Christopher J.,De Gombert, Antoine,McKay, Alasdair I.,Wheelhouse, Katherine M.,Willis, Michael C.
supporting information, (2020/02/25)
Pyridine and related heterocyclic sulfinates have recently emerged as effective nucleophilic coupling partners in palladium-catalyzed cross-coupling reactions with (hetero)aryl halides. These sulfinate reagents are straightforward to prepare, stable to storage and coupling reaction conditions, and deliver efficient reactions, thus offering many advantages, compared to the corresponding boron-derived reagents. Despite the success of these reactions, there are only scant details of the reaction mechanism. In this study, we use structural and kinetic analysis to investigate the mechanism of these important coupling reactions in detail. We compare a pyridine-2-sulfinate with a carbocyclic sulfinate and establish different catalyst resting states, and turnover limiting steps, for the two classes of reagent. For the carbocyclic sulfinate, the aryl bromide oxidative addition complex is the resting state intermediate, and transmetalation is turnover-limiting. In contrast, for the pyridine sulfinate, a chelated Pd(II) sulfinate complex formed post-transmetalation is the resting-state intermediate, and loss of SO2 from this complex is turnover-limiting. We also investigated the role of the basic additive potassium carbonate, the use of which is crucial for efficient reactions, and deduced a dual function in which carbonate is responsible for the removal of free sulfur dioxide from the reaction medium, and the potassium cation plays a role in accelerating transmetalation. In addition, we show that sulfinate homocoupling is responsible for converting Pd(OAc)2 to a catalytically active Pd(0) complex. Together, these studies shed light on the challenges that must be overcome to deliver improved, lower temperature versions of these synthetically important processes.
Alkene synthesis: Elimination of arenesulfinic acid from alkyl aryl sulfones using potassium trimethylsilanolate as base
Baker-Glenn, Charles A.G.,Barrett, Anthony G.M.,Gray, Andrew A.,Procopiou, Panayiotis A.,Ruston, Mark
, p. 7427 - 7430 (2007/10/03)
The use of potassium trimethylsilanolate as base to induce elimination of potassium arenesulfinate from alkyl aryl sulfones to produce E-alkenes is described. The reaction was appropriate for substrates containing a benzyl or allyl group α to the sulfone
DONOR SUBSTITUTED SULFONYL CARBENES - 1. METHOXY ARYLSULFONYL CARBENES
Schank, Kurt,Abdel Wahab, Aboel-Magd A.,Eigen, Peter,Jager, Juergen
, p. 6667 - 6678 (2007/10/02)
Alkoxy arylsulfonyl carbenes 3 are generated by α elimination of hydrogen halide from (alkoxy)(halogeno)methyl aryl sulfones 1.Their self-decomposition as well as trapping reactions with diazoalkanes and with appropriate olefins are described.The structures of obtained cyclopropanes 21 and 23 are elucidated by 1H NMR methods.
Reaction of Organic Sulfur Compounds with Hyperoxide Anion (O2-anion radical). IV. Evidence for Formation of Peroxysulfur Intermediates: Oxidation of Sulfoxides, Phosphines, and Olefins with Intermediary Peroxysulfur Species
Oae, Shigeru,Takata, Toshikazu,Kim, Yong Hae
, p. 2712 - 2723 (2007/10/02)
Formations of peroxy-sulfenate(I), -sulfinate(II), and -sulfonate(III) as intermediates have been confirmed by stripping the peroxy oxygen with three kinds of trapping agents such as sulfoxides, phosphines, and olefins, added in the reaction systems of various organic sulfur compounds with hyperoxide anion (O2-anion radical).These sulfoxides, phosphines, and olefins were inert to O2-anion radical alone while electrophilic olefins, such as α,β-unsaturated ketones reacted readily with O2-anion radical to afford the carboxylic acid.Sulfoxides, added into the reaction system of disulfide, thiosulfinic S-ester, thiosulfonic S-ester, or sulfonyl chloride with O2-anion radical, were found to be oxidized to the sulfones with peroxysulfur intermediates formed in situ in the system.Phosphines, added into the reaction system of disulfide or sodium thiolate with O2-anion radical were also oxidized to the phosphine oxides.Not only stilbene and acenaphthylene but also chalcone and its derivatives, placed in the reactions of sulfonyl chloride, sulfinyl chloride and thiosulfonic S-ester with O2-anion radical were found to be oxidized to the corresponding epoxides.These observations suggest clearly that the intermediary peroxysulfur compounds can act as oxidizing agents which oxidize these trapping agents by the nucleophilic oxygenative oxidation.Similar intermediates were postulated and confirmed in the alkaline autoxidations of thiol and disulfide in which added phosphines and sulfoxides were also found to be oxidized to their oxides.The mechanisms of the reactions of these trapping agents with peroxysulfur intermediates are discussed.
Unusual Base-induced Ring-opening Reactions of the Bis-tosylhydrazones of Dibenzobicyclooctadiene-2,3-dione and Acenaphthenequinone
Nakayama, Juzo,Segiri, Tsunehiko,Ohya, Ryuji,Hoshino, Masamatsu
, p. 791 - 792 (2007/10/02)
Unusual KOH-induced ring-opening reactions of the bis-tosylhydrazones of dibenzobicyclooctadiene-2,3-dione and acenaphthenequinone are described.
