Expedient Synthesis of Sulfinamides from Sulfonyl Chlorides

Harmata, Michael; Zheng, Pinguan; Huang, Chaofeng; Gomes, Maria G.; Ying, Weijiang; Ranyanil, Kanok-On; Balan, Gayatri; Calkins, Nathan L.

doi:10.1021/jo062296i

Cited by 102 publications

(52 citation statements)

References 23 publications

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“…[33] The reactivity of the catalyst was also compared with that of commercially available MgO (surface area: 25 m 2 g À1 ) and MgO-supported activated carbon with high specific surface area. It was observed that a mere 20 % of the desired product could be isolated when commercial MgO was used as the catalyst in the reaction of ptoluenesulfonyl chloride with benzylamine in the presence of triphenylphosphine as reducing agent.…”

Section: Resultsmentioning

confidence: 99%

“…The products were identified by NMR spectroscopy and mass spectrometry and the results were compared with data available in the literature. [33] The data for a representative example are given below.…”

Section: Methodsmentioning

confidence: 99%

“…To render this reaction more useful in the area of sulfinamide chemistry, an elegant single-step process is desired. [33] Recently, much effort has been directed towards a mild synthesis of sulfinamides. Sharpless and Klunder reported the synthesis of sulfinate esters from sulfonyl chlorides by a one-pot reductive esterification reaction using phosphites as the reducing agent.…”

Section: Introductionmentioning

confidence: 99%

“…[35] Recently, Harmata et al have reported the synthesis of sulfinamides from sulfonyl chlorides, with triphenylphosphine as a reductant and triethylamine as the base. [33] Unfortunately, most of the synthetic methods developed so far for the preparation of sulfinamides are homogeneously catalyzed processes, which have several disadvantages such as difficulty in separation of the product from the reaction mixture, poor recyclability, and the requirement for a stoichiometric amount of catalyst. To the best of our knowledge, no reports of the heterogeneously catalyzed synthesis of sulfinamides from the corresponding sulfonyl chlorides are available in the literature.…”

Section: Introductionmentioning

confidence: 99%

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Functionalization of Mesoporous Carbon with Superbasic MgO Nanoparticles for the Efficient Synthesis of Sulfinamides

Chakravarti

Mano

Iwaï³

et al. 2011

Chemistry A European J

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Highly basic MgO nanoparticles with different sizes have been successfully immobilized over mesoporous carbon with different pore diameters by a simple wet-impregnation method. The prepared catalysts have been characterized by various sophisticated techniques, such as XRD, nitrogen adsorption, electron energy loss spectroscopy, high-resolution TEM, X-ray photoelectron spectroscopy, and the temperature-programmed desorption of CO(2). XRD results reveal that the mesostructure of the support is retained even after the huge loading of MgO nanoparticles inside the mesochannels of the support. It is also demonstrated that the particle size and dispersion of the MgO nanoparticles on the support can be finely controlled by the simple adjustment of the textural parameters of the supports. Among the support materials studied, mesoporous carbon with the largest pore diameter and large pore volume offered highly crystalline small-size cubic-phase MgO nanoparticles with a high dispersion. The basicity of the MgO-supported mesoporous carbons can also be controlled by simply changing the loading of the MgO and the pore diameter of the support. These materials have been employed as heterogeneous catalysts for the first time in the selective synthesis of sulfinamides. Among the catalysts investigated, the support with the large pore diameter and high loading of MgO showed the highest activity with an excellent yield of sulfinamides. The catalyst also showed much higher activity than the pristine MgO nanoparticles. The effects of the reaction parameters, including the solvents and reaction temperature, and textural parameters of the supports in the activity of the catalyst have also been demonstrated. Most importantly, the catalyst was found to be highly stable, showing excellent activity even after the third cycle of reaction.

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Section: Resultsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Functionalization of Mesoporous Carbon with Superbasic MgO Nanoparticles for the Efficient Synthesis of Sulfinamides

Chakravarti

Mano

Iwaï³

et al. 2011

Chemistry A European J

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“…[50][51][52][53][54][55][56][57][58] Their use in chemistry relies mainly on their facile chemical reduction, [50][51][52][53][54][55][56][57][58] which has been shown to lead to various products through a reaction with a wide range of reagents, and on the readiness to replace the Cl with various substituents. [50][51][52][53][54][55][56][57][58] Despite this wide use of sulfonyl chlorides under reductive conditions, the ET to these compounds and the factors controlling it are still not well understood. A number of electrochemical investigations have been reported in different media but a clear picture of the details of the reduction mechanism is still lacking.…”

Section: Introductionmentioning

confidence: 99%

Application of the dissociative electron transfer theory and its extension to the case of in-cage interactions in the electrochemical reduction of arenesulfonyl chlorides

Houmam

Hamed

2012

Phys. Chem. Chem. Phys.

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Important aspects of the electrochemical reduction of a series of substituted arene sulfonyl chlorides are investigated. An interesting autocatalytic mechanism is encountered where the starting material is reduced both at the electrode and through homogeneous electron transfer from the resulting sulfinate anion. This is due to the homogenous electron transfer from the two-electron reduction produced anion (arene sulfinate) to the parent arene sulfonyl chloride. As a result, the reduction process and hence the generated final products depend on both the concentration of the substrate and the scan rate. A change is also observed in the reductive cleavage mechanism as a function of the substituent on the phenyl ring of the arene sulfonyl chloride. With 4-cyano and 4-nitrophenyl sulfonyl chlorides a "sticky" dissociative ET mechanism takes place where a concerted ET mechanism leads to the formation of a radical/anion cluster before decomposition. With other substituents (MeO, Me, H, Cl, and F) a "classical" dissociative ET is followed, where the ET and bond cleavage are simultaneous. The dissociative electron transfer theory, as well as its extension to the case of strong in-cage interactions between the produced fragments, along with gas phase chemical quantum calculations results helped us to rationalize both the observed change in the ET mechanism and the occurrence of the "sticky" dissociative ET mechanism. The radical/anion pair interactions have been determined both in solution as well as in the gas phase. The study also shows that despite the low magnitude of in-cage interactions in acetonitrile compared to the gas phase their existence strongly affects the dynamics of the involved reactions. It also shows that, as expected, these interactions are reinforced by the existence of strong electron-withdrawing substituents. The occurrence of an autocatalytic process and the existence of the radical/anion interaction may explain the differences previously observed in the reduction of these compounds in different media.

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A Facile and Efficient Approach to N‐Protected‐β‐Sulfinyl‐ enamines via C‐Sulfinylation of Enamides and Enecarbamates

Cheng

et al. 2010

Adv Synth Catal

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A practical method has been developed for the C-sulfinylation of enamides and enecarbam-A C H T U N G T R E N N U N G ates using sodium phenylsulfinate/methyltrichloro-A C H T U N G T R E N N U N G silane (PhSO 2 Na/MeSiCl 3 ) as the sulfinylating reagent and N,N-dimethylacetamide (DMAc) as the Lewis base promoter, which allows for the preparation of a variety of N-protected-b-sulfinylenamines in high yields and good stereoselectivities. The Lewis base is found to be important for both the in situ generation of the active sulfinylating species (PhSOCl) and the sulfinylation step.Keywords: enamides; enecarbamates; Lewis base; sodium phenylsulfinate/methyltrichlorosilane (PhSO 2 Na/MeSiCl 3 ); C-sulfinylation Organic sulfoxides are an important class of compounds that have found broad applications.[1] They serve as key structural components in some drug molecules.[2] Chiral sulfoxides are well known chiral auxiliaries and ligands for asymmetric synthesis.[3] Besides the oxidation of sulfides, [4] the sulfinylation of organometallic nucleophiles (Li, [5] Cu, [6] Zn, [7] and Mg [8] reagents) with sulfinates represents the most important method for the preparation of sulfoxides, which, however, suffers from limited practicality due to the use of relatively expensive organometallics that typically require low temperature and moisture-free conditions. Sulfinylation of organometallics-free carbon nucelophiles with sulfinyl chloride is in principle a more practical and cost-efficient method. Although the Osulfinylation [9] of alcohols and the N-sulfinylation [10] of amines with sulfinyl chloride are well-known and efficient approaches to sulfinates and sulfinamides, respectively, so far there have been no effective methods available for the C-sulfinylation of organic carbon nucleophiles to synthesize sulfoxides. Glaros [11] and Lavilla [12] have reported that ketones and dihydropyridines can be directly sulfinylated with sulfinyl chloride to produce sulfoxide derivatives which, however, only give low yields. Herein, we present the first highly effective method for C-sulfinylation of enamides and enecarbamates with in situ generated phenyl sulfinyl chloride (PhSOCl), which allows for the preparation of N-protected-b-sulfinylenamines in high yields (up to 99%) and good stereoselectivities.Recently, in an attempt to use in situ generated enecarbamate 1a from 1a' as the nucleophile for chlorosilane-promoted Mannich-type reactions, [13] a new compound 2a was obtained as a by-product (Scheme 1). We speculated that this side reaction should be due to the nucleophilic attack of the enecarbamate 1a to an active sulfinyl species. To explore if such a side reaction could be developed into a useful new method for the preparation of functionalized vinyl sulfoxides, we directly treated isolated 1a with sodium phenylsufinate (PhSO 2 Na) and SiCl 4 in the presence of DMF in dry CH 2 Cl 2 . To our delight, the desired product 2a was achieved in 92% yield in 1.5 h (entry 1, Table 1).Scheme 1. Observed C-sulfinylation of enecarbam...

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Expedient Synthesis of Sulfinamides from Sulfonyl Chlorides

Cited by 102 publications

References 23 publications

Functionalization of Mesoporous Carbon with Superbasic MgO Nanoparticles for the Efficient Synthesis of Sulfinamides

Functionalization of Mesoporous Carbon with Superbasic MgO Nanoparticles for the Efficient Synthesis of Sulfinamides

Application of the dissociative electron transfer theory and its extension to the case of in-cage interactions in the electrochemical reduction of arenesulfonyl chlorides

A Facile and Efficient Approach to N‐Protected‐β‐Sulfinyl‐ enamines via C‐Sulfinylation of Enamides and Enecarbamates

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