- A FACILE SYNTHESIS OF SULFINYL CHLORIDES FROM THIOLACETATES
-
Alkyl and aryl thiolacetates are converted smoothly into sulfinyl chlorides by sulfuryl chloride in the presence of acetic anhydride.
- Thea, Sergio,Cevasco, Giorgio
-
-
Read Online
- Regio- and Stereoselective Chloro Sulfoximidations of Terminal Aryl Alkynes Enabled by Copper Catalysis and Visible Light
-
By visible-light photoredox catalysis with copper complexes, sulfoximidoyl chlorides add to terminal aryl alkynes to give the corresponding (E)-β-chlorovinyl sulfoximines with exclusive regio- and stereoselectivities in high yields. Two representative pro
- Shi, Peng,Tu, Yongliang,Zhang, Duo,Wang, Chenyang,Truong, Khai-Nghi,Rissanen, Kari,Bolm, Carsten
-
supporting information
p. 2552 - 2556
(2021/03/19)
-
- Direct conversion of sulfinamides to thiosulfonates without the use of additional redox agents under metal-free conditions
-
Direct conversion of sulfinamides to thiosulfonates is described. Without the use of additional redox agents, the reaction proceeds smoothly in the presence of TFA under metal-free conditions. This protocol possesses many advantages such as odourless and stable starting materials, broad substrate scope, selective synthesis, and mild reaction conditions. This journal is
- Ji, Yuan-Zhao,Li, Hui-Jing,Wang, Jun-Hu,Wu, Yan-Chao,Zhang, Chi
-
supporting information
p. 9291 - 9298
(2021/11/13)
-
- General Method for the Asymmetric Synthesis of N-H Sulfoximines via C-S Bond Formation
-
A versatile method for the synthesis of enantioenriched N-H sulfoximines is reported. The approach stems from the organomagnesium-mediated ring opening of novel cyclic sulfonimidate templates. The reactions proceed in high yield and with excellent stereofidelity with alkyl, aryl, and heteroaryl Grignard reagents. The chiral auxiliary is readily removed from the resultant sulfoximines via an unusual oxidative debenzylation protocol that utilizes molecular oxygen as the terminal oxidant. This provides a general strategy for the synthesis of highly enantioenriched N-H sulfoximines.
- Argent, Stephen P.,Lewis, William,Mendon?a Matos, Priscilla,Moore, Jonathan c.,Stockman, Robert A.
-
supporting information
(2020/03/30)
-
- Rapid Deoxyfluorination of Alcohols with N-Tosyl-4-chlorobenzenesulfonimidoyl Fluoride (SulfoxFluor) at Room Temperature
-
The deoxyfluorination of alcohols is a fundamentally important approach to access alkyl fluorides, and thus the development of shelf-stable, easy-to-handle, fluorine-economical, and highly selective deoxyfluorination reagents is highly desired. This work describes the development of a crystalline compound, N-tosyl-4-chlorobenzenesulfonimidoyl fluoride (SulfoxFluor), as a novel deoxyfluorination reagent that possesses all of the aforementioned merits, which is rare in the arena of deoxyfluorination. Endowed by the multi-dimensional modulating ability of the sulfonimidoyl group, SulfoxFluor is superior to 2-pyridinesulfonyl fluoride (PyFluor) in fluorination rate, and is also superior to perfluorobutanesulfonyl fluoride (PBSF) in fluorine-economy. Its reaction with alcohols not only tolerates a wide range of functionalities including the more sterically hindered alcoholic hydroxyl groups, but also exhibits high fluorination/elimination selectivity. Because SulfoxFluor can be easily prepared from inexpensive materials and can be safely handled without special techniques, it promises to serve as a practical deoxyfluorination reagent for the synthesis of various alkyl fluorides.
- Guo, Junkai,Kuang, Cuiwen,Rong, Jian,Li, Lingchun,Ni, Chuanfa,Hu, Jinbo
-
supporting information
p. 7259 - 7264
(2019/05/10)
-
- N-Trifluoromethylthiolated Sulfonimidamides and Sulfoximines: Anti-microbial, Anti-mycobacterial, and Cytotoxic Activity
-
Herein we demonstrate the expanded utility of a recently described N-trifluoromethylthiolation protocol to sulfonimidamide containing substances. The novel N-trifluoromethylthio sulfonimidamide derivatives thus obtained were evaluated for antibacterial activity against Mycobacterium tuberculosis (M. tb.) and Mycobacterium abscessus and Gram + Ve (Streptococcus aureus, Bacillus subtilis), and Gram - Ve (Escherichia coli, Pseudomonas aeruginosa) bacteria. Two compounds, 13 and 15 showed high antimycobacterial activity with MIC value of 4-8 μg/mL; i.e. comparable to WHO recommended first line antibiotic for TB infection ethambutol. The same compounds were also found to be cytotoxic in HepG2 cells (compound 13 IC50 = 15 μg/mL; compound 15 IC50 = 65 μg/mL). A structure activity relationship, using matched pair analysis, gave the unexpected conclusion that the trifluoromethylthio moiety was responsible for the cellular and bacterial toxicity. Given the increasing use of the trifluoromethylthio group in contemporary medicinal chemistry, this observation calls for considerations before implementation of the functionality in drug design.
- Thota, Niranjan,Makam, Parameshwar,Rajbongshi, Kamal K.,Nagiah, Savania,Abdul, Naeem Sheik,Chuturgoon, Anil A,Kaushik, Amit,Lamichhane, Gyanu,Somboro, Anou M.,Kruger, Hendrik G.,Govender, Thavendran,Naicker, Tricia,Arvidsson, Per I
-
supporting information
p. 1457 - 1461
(2019/10/11)
-
- Sulfinate-Organocatalyzed (3+2) Annulation Reaction of Propargyl or Allenyl Sulfones with Activated Imines
-
An operationally simple methodology for the synthesis of 4-sulfonyl-3-pyrrolines is described using a propargylic sulfone and N-sulfonyl imines as substrates. This annulation process is initiated by an arenesulfinate organocatalyst, which allows a smooth isomerization of the alkynyl precursor into the corresponding allene, followed by the generation of a highly reactive allyl sulfone anion. An asymmetric version involving an unprecedented enantiopure sulfinate–ammonium cooperative ion pair (PhSO2– R4N+*) was investigated. A proof-of-concept, with enantiomeric excesses of up to 41 %, was obtained according to a preliminary screening of commercially available chiral phase-transfer catalysts.
- Martzel, Thomas,Lohier, Jean-Fran?ois,Gaumont, Annie-Claude,Brière, Jean-Fran?ois,Perrio, Stéphane
-
supporting information
p. 5069 - 5073
(2018/09/14)
-
- Sulfinate-Organocatalyzed (3+2) Annulation of Allenyl Sulfones with 1,1-Dicyano Olefins in the Presence of a Quaternary Ammonium Phase Transfer Agent
-
The benzenesulfinate-catalyzed (3+2) annulation between allenyl sulfones and aryl(alkyl)idenemalononitriles has been developed under mild phase transfer conditions, affording a breadth of functionalized sulfonyl cyclopentenes in good to excellent yields (
- Martzel, Thomas,Lohier, Jean-Fran?ois,Gaumont, Annie-Claude,Brière, Jean-Fran?ois,Perrio, Stéphane
-
supporting information
p. 2696 - 2706
(2018/07/29)
-
- Sulfonimidates: Useful Synthetic Intermediates for Sulfoximine Synthesis via C-S Bond Formation
-
Medicinally relevant sulfoximines are accessed from C-S coupling of sulfonimidates and commercially available organomagnesium reagents. Sulfonimidates are conveniently synthesized by oxidative alkoxylation of readily available sulfinamides. This constitutes a general C-S coupling approach for the synthesis of sulfoximines.
- Matos, Priscilla Mendon?a,Lewis, William,Moore, Jonathan C.,Stockman, Robert A.
-
supporting information
p. 3674 - 3677
(2018/06/26)
-
- One-pot synthesis of α-phenylsulfinyl ketones by reaction of phenyl benzenethiosulfinate with enolate anions, and synthesis of sulfoxides and sulfides by its reaction with Grignard reagents
-
Phenyl benzenethiosulfinate reacts with enolate anions derived from ketones to give α-phenylsulfinyl ketones directly, together with minor amounts of α-phenylsulfanyl ketones. These are easily separated by forming the water-soluble sodium salts of the sulfinyl compounds. Grignard reagents also react with phenyl benzenethiosulfinate, to give mixtures of sulfoxides and sulfides.
- Fakhry, Jerome,Grayson, David H.
-
p. 556 - 563
(2017/12/28)
-
- Unique Reactivity of α-Substituted Electron-Deficient Allenes using Sulfinate Salts as Lewis Base Organocatalysts
-
The efficient sulfinate-catalyzed intermolecular addition reaction of α-substituted allenyl sulfones and allenoates with Michael acceptors is highlighted. The sequence proceeds under mild conditions to provide a scalable and efficient access to versatile
- Martzel, Thomas,Lohier, Jean-Fran?ois,Gaumont, Annie-Claude,Brière, Jean-Fran?ois,Perrio, Stéphane
-
supporting information
p. 96 - 106
(2017/01/14)
-
- A New, Practical One-Pot Synthesis of Unprotected Sulfonimidamides by Transfer of Electrophilic NH to Sulfinamides
-
Unprotected tertiary sulfonimidamides have been prepared in good to excellent yields in a one-pot transformation from tertiary sulfinamides through NH transfer. The reaction is mediated by commercially available (diacetoxyiodo)benzene and ammonium carbamate in methanol under convenient conditions. A wide range of functional groups are tolerated and initial results indicate that the NH transfer is stereospecific. A small molecule X-ray analysis of NH sulfonimidamide 2 a and its behavior in selected in vitro assays in comparison to the matched sulfonamide are also reported. This new reaction provides a safe, short and efficient approach to sulfonimidamides, which have been the subject of recent, growing interest in the life sciences.
- Izzo, Flavia,Sch?fer, Martina,Stockman, Robert,Lücking, Ulrich
-
supporting information
p. 15189 - 15193
(2017/10/12)
-
- Design, synthesis and evaluation of new GEQ derivatives as inhibitors of InhA enzyme and Mycobacterium tuberculosis growth
-
A series of fluorene-based derivatives was synthesized and evaluated for inhibiting both InhA and Mycobacterium tuberculosis growth. These compounds were inspired by the previously reported Genz-10850 molecule, a good InhA inhibitor, but with a poor activity against M. tuberculosis growth. Structure-activity relationships were performed by introducing the following chemical modifications: 1) the piperazine ring; 2) the amide group; 3) the aryl moiety; and 4) the fluorene moiety. Among these new derivatives, one of them was more effective against both the InhA activity and mycobacterial growth, compared to the hit compound. Docking studies were also performed to rationalize activities of these derivatives. Furthermore, we showed for the first time that efflux pump inhibitors potentiated the efficacy of Genz-10850 (GEQ) derivatives against M. tuberculosis growth, demonstrating that these compounds could be substrates of some efflux pumps.
- Chollet, Aurélien,Mori, Giorgia,Menendez, Christophe,Rodriguez, Frédéric,Fabing, Isabelle,Pasca, Maria Rosalia,Madacki, Jan,Korduláková, Jana,Constant, Patricia,Quémard, Anna?k,Bernardes-Génisson, Vania,Lherbet, Christian,Baltas, Michel
-
p. 218 - 235
(2015/07/07)
-
- Synthesis and arylation of unprotected sulfonimidamides
-
Herein we evaluate different methodologies for the synthesis of unprotected sulfonimidamides. Three different procedures that allow orthogonal deprotection of the imine nitrogen under acidic, nucleophilic, and basic conditions were established. Moreover,
- Funes Maldonado, Matías,Sehgelmeble, Fernando,Bjarnemark, Fanny,Svensson, Mats,?hman, Jens,Arvidsson, Per I.
-
experimental part
p. 7456 - 7462
(2012/09/22)
-
- Synthesis of CF3-substituted sulfoximines from sulfonimidoyl fluorides
-
N-Protected trifluoromethyl-substituted sulfoximines have been prepared by treatment of sulfonimidoyl fluorides with a combination of the Ruppert-Prakash reagent (TMSCF3) and tetrabutyl ammonium fluoride (TBAF). The starting materials were accessed following two synthetic routes, and for each reaction sequence the substrate scope was evaluated. Accordingly, a wide variety of aryl-substituted products were obtained in moderate to good yield.
- Kowalczyk, Rafal,Edmunds, Andrew J. F.,Hall, Roger G.,Bolm, Carsten
-
supporting information; experimental part
p. 768 - 771
(2011/04/24)
-
- Practical and highly stereoselective method for the preparation of several chiral arylsulfinamides and arylsulfinates based on the spontaneous crystallization of diastereomerically pure N-benzyl-N-(1-phenylethyl)- arylsulfinamides
-
A novel and simple process for the preparation of enantiomerically pure (SS)-benzenesulfinamide (SS)-3a, (SS)-p- toluenesulfinamide (SS)-3b, (SS)-p-chloro- benzenesulfinamide (SS)-3c and (SS)-p- fluorobenzenesulfinamide (SS)-3d has been developed. The treatment of arylsulfinyl chlorides with (R)-N-benzyl-1-phenylethanamine in the presence of excess triethylamine gave diastereomeric mixtures of N-benzyl-N-(1-phenylethyl)- arylsulfinamides 1, which underwent spontaneous crystallization to furnish diastereomerically pure (R,SS)-N-benzyl-N-(1-phenylethyl)- arylsulfinamides (R,SS)-1a-1d in 28%, 29%, 27% and 31% yields, respectively. The diastereomerically pure compounds (R,SS)-1 were then converted into four enantiopure (RS)-methyl arylsulfinates (RS)-2, and finally into four enantiopure (SS)- arylsulfinamides (SS)-3 in good yields.
- Zhu, Rui-Heng,Shi, Xiao-Xin
-
experimental part
p. 387 - 393
(2011/06/11)
-
- C2-symmetric chiral disulfoxide ligands in rhodium-catalyzed 1,4-addition: From ligand synthesis to the enantioselection pathway
-
A family of chiral C2-symmetric disulfoxide ligands possessing biaryl atropisomeric backbones has been synthesized by using the Andersen methodology. Complete characterization includes X-ray crystallographic studies of all ligands and some of t
- Mariz, Ronaldo,Poater, Albert,Gatti, Michele,Drinkel, Emma,Buergi, Justus J.,Luan, Xinjun,Blumentritt, Sascha,Linden, Anthony,Cavallo, Luigi,Dorta, Reto
-
supporting information; experimental part
p. 14335 - 14347
(2011/03/22)
-
- Further explorations on bridged 1,2,4-trioxanes
-
Three new bicyclo[3.2.1]-type 1,2,4-trioxanes have been designed and synthesized. One of them demonstrates better tolerance of the intramolecular hemiketals to steric crowding in hydroperoxidation. The other represents a prototype for possible manipulation of the transient radicals generated in cleavage reactions. A new substitution pattern in the bridged system is explored through synthesis of the third molecule. The configurations of all stereogenic centers in the bridged system can be effectively controlled by the chirality of the allyl alcohol as illustrated by the enantioselective synthesis of the fourth molecule. Finally, similar bicyclo[3.3.1]-type 1,2,4-trioxanes are shown very difficult to be synthesized because of the involvement of a conformer with two substituents at axial positions at the same time.
- Zhang, Qi,Wu, Yikang
-
p. 10189 - 10201
(2008/02/13)
-
- Efficient synthesis of carbohydrate thionolactones
-
Carbohydrate thionolactones may be efficiently synthesized from the corresponding 1-thio sugars via a two-step procedure involving formation of a glycosyl phenylthiosulfinate by treatment with either phenylsulfinyl chloride or 1-(phenylsulfinyl)piperidine
- Chayajarus, Kampanart,Fairbanks, Antony J.
-
p. 3517 - 3520
(2007/10/03)
-
- Improved synthesis of 1-benzenesulfinyl piperidine and analogs for the activation of thioglycosides in conjunction with trifluoromethanesulfonic anhydride
-
An improved protocol for the large-scale production of 1-benzenesulfinyl piperidine and other sulfinamides is described. It is demonstrated that 1-benzenesulfinyl pyrrolidine and N,N-diethyl benzenesulfinamide function analogously to 1-benzenesulfinyl pip
- Crich, David,Banerjee, Abhisek,Li, Wenju,Yao, Qingjia
-
p. 415 - 424
(2007/10/03)
-
- Platelet ADP receptor inhibitors
-
Novel compounds of formulae (I) to (VIII), which more particularly include sulfonylurea derivatives, sulfonylthiourea derivatives, sulfonylguanidine derivatives, sulfonylcyanoguanidine derivatives, thioacylsulfonamide derivatives, and acylsulfonamide derivatives which are effective platelet ADP receptor inhibitors. These derivatives may be used in various pharmaceutical compositions, and are particularly effective for the prevention and/or treatment of cardiovascular diseases, particularly those diseases related to thrombosis. The invention also relates to a method for preventing or treating thrombosis in a mammal comprising the step of administering a therapeutically effective amount of a compound of formulae (I) to (VIII), or a pharmaceutically acceptable salt thereof.
- -
-
-
- Platelet ADP receptor inhibitors
-
Novel compounds of formulae (I) to (VIII), which more particularly include sulfonylurea derivatives, sulfonylthiourea derivatives, sulfonylguanidine derivatives, sulfonylcyanoguanidine derivatives, thioacylsulfonamide derivatives, and acylsulfonamide derivatives which are effective platelet ADP receptor inhibitors. These derivatives may be used in various pharmaceutical compositions, and are particularly effective for the prevention and/or treatment of cardiovascular diseases, particularly those diseases related to thrombosis. The invention also relates to a method for preventing or treating thrombosis in a mammal comprising the step of administering a therapeutically effective amount of a compound of formulae (I) to (VIII), or a pharmaceutically acceptable salt thereof.
- -
-
-
- A new method for oxidation of various alcohols to the corresponding carbonyl compounds by using n-t-butylbenzenesulfinimidoyl chloride
-
Various primary and secondary alcohols were smoothly oxidized to the corresponding aldehydes and ketones by using a new oxidizing agent, N-t-butylbenzenesulfinimidoyl chloride (4a), in the coexistence of DBU or zinc oxide. The present oxidation proceeded under mild conditions via five-membered intramolecular proton-transfer of an alkyl arenesulfinimidate intermediate.
- Matsuo, Jun-Ichi,Iida, Daisuke,Tatani, Kazuya,Mukaiyama, Teruaki
-
p. 223 - 234
(2007/10/03)
-
- Convenient method for the preparation of aryl sulfinyl chlorides
-
Reaction of activated arenes with thionyl chloride in the presence of montmorillonite K-10 clay affords the corresponding aryl sulfinyl chlorides in good yield.
- Karade,Kate,Adude
-
p. 1573 - 1574
(2007/10/03)
-
- Oxidative fragmentations of 2-(trimethylsilyl)ethyl sulfoxides - Routes to alkane-, arene-, and highly substituted 1-alkenesulfinyl chlorides
-
The preparation of a collection of alkyl, aryl, and 1-alkenyl 2-(trimethylsilyl)ethyl sulfoxides is outlined, using mostly vinyltrimethylsilane or 2-(trimethylsilyl)ethanesulfenyl chloride (5) as key starting materials. The 2-(trimethylsilyl)ethyl group can be cleaved from many of the sulfoxides under oxidative fragmentation conditions using sulfuryl chloride and the reaction represents a new protocol for sulfinyl chloride synthesis. The method is suitable for most alkane- and arenesulfinyl chlorides (3), but is limited to highly substituted vinylic sulfinyl chlorides. 1-Alkenyl 2-(trimethylsilyl)ethyl sulfoxides with reduced double bond substitution (6, 7, 11) succumb to reactions involving chlorination of the double bond. The β-effect of silicon is invoked to explain the ability of the 2-(trimethylsilyl)ethyl group to induce C-S bond scission under the oxidative cleavage reaction conditions. A mechanism is offered to account for the role played by the β-silicon atom of the 2-(trimethylsilyl)ethyl group. Indeed, the silicon atom is self-sacrificial in that it diverts the course of the reaction from the usual α-carbon chlorination mode to one of oxidative cleavage, whereby the 2-(trimethylsilyl)ethyl group is lost. The overall reaction calls upon the ability of silicon atoms to donate electron density by hyperconjugation.
- Schwan, Adrian L.,Strickler, Rick R.,Dunn-Dufault, Robert,Brillon, Denis
-
p. 1643 - 1654
(2007/10/03)
-
- S-(4-methoxyphenyl) benzenethiosulfinate (MPBT)/ trifluoromethanesulfonic anhydride: A convenient system for the generation of glycosyl triflates from thioglycosides
-
(Matrix presented) The combination of S-(4-methoxyphenyl) benzenethiosulfinate (MPBT, 1) and trifluoromethanesulfonic anhydride forms a powerful, metal-free, thiophile which readily activates thioglycosides, via glycosyl triflates, at -60°C in dichloromet
- Crich, David,Smith, Mark
-
p. 4067 - 4069
(2007/10/03)
-
- Sulfonimidamide analogs of oncolytic sulfonylureas
-
A series of sulfonimidamide analogs of the oncolytic diarylsulfonylureas was synthesized and evaluated for (1) in vitro cytotoxicity against CEM cells, (2) in vivo antitumor activity against subaxillary implanted 6C3HED lymphosarcoma, and (3) metabolic breakdown to the o-sulfate of p- chloroaniline. The separated enantiomers of one sulfonimidamide analog displayed very different activities in the in vivo screening model. In general, several analogs demonstrated excellent growth inhibitory activity in the 6C3HED model when dosed orally or intraperitoneally. A correlative structure-activity relationship to the oncolytic sulfonylureas was not apparent.
- Toth, John E.,Grindey, Gerald B.,Ehlhardt, William J.,Ray, James E.,Boder, George B.,Bewley, Jesse R.,Klingerman, Kim K.,Gates, Susan B.,Rinzel, Sharon M.,Schultz, Richard M.,Weir, Leonard C.,Worzalla, John F.
-
p. 1018 - 1025
(2007/10/03)
-
- Novel ipso-Substitution of p-Sulfinylphenols through the Pummerer-Type Reaction: A Selective and Efficient Synthesis of p-Quinones and Protected p-Dihydroquinones
-
The treatment of p-sulfmylphenols 3a-q with trifluoroacetic anhydride caused a Pummerer-type reaction on aromatic rings and concomitant desulfurization to give mixtures of the corresponding p-dihydroquinones 9 and p-quinones 10, which were subsequently oxidized under mild conditions to provide high yields of p-quinones 10. On the other hand, the treatment of p-(phenylsulfinyl)-phenyl ethers 6 with trifluoroacetic anhydride in the presence of styrene caused the direct ipso-substitution of the sulfinyl groups into trifluoroacetoxy groups, giving the protected dihydroquinones 14 in high yields. Both types of reactions were generally completed below room temperature within 1 h and compatible with various functional groups such as the allyl, carbonyl, ester, amide, and silyloxy groups. The preparation of the p-sulfmylphenols 3 and the silyl ethers 6 is also described through p-specific thiocyanation of phenols followed by the Grignard reaction and oxidation.
- Akai, Shuji,Takeda, Yoshifumi,Iio, Kiyosei,Takahashi, Kenji,Fukuda, Nobuhisa,Kita, Yasuyuki
-
p. 5526 - 5536
(2007/10/03)
-
- Nitrosations with hydrazine derivatives: Synthesis of N4-arenesulfinylsemicarbazides and N5-arenesulfinyl-N1-aminobiuretes from arenesulfinylisocyanates and N,N-disubstituted hydrazines
-
Arenesulfinyl-isocyanates 5 prepared in situ from arenesulfinyl chlorides 4 and silver cyanate react with N,N-disubstituted hydrazines to mixtures of N4-arenesulfinylsemicarbazides 6 as main components and N5-arenesulfinyl-N1/s
- Hanefeld,Landwehr
-
p. 344 - 351
(2007/10/02)
-
- Sulfinyl chlorides through the oxidative chlorination of sulfenyl derivatives with trimethylsilyl acetate/sulfuryl chloride system
-
A new and useful procedure for the synthesis of sulfinyl chlorides is described involving a combined action of trimethylsilyl acetate and sulfuryl chloride as a oxidative chlorination system on sulfenyl derivatives.
- Drabowicz,Bujnicki,Dudzinski
-
p. 1207 - 1213
(2007/10/02)
-
- Additive Pummerer reactions of vinylic sulfoxides. Synthesis of γ-hydroxy-α,β-unsaturated esters, α-hydroxyketones, and 2-phenylsulfenyl aldehydes and primary alcohols
-
Treatment of β-monosubstituted vinylic sulfoxides 1 with trifluoroacetic anhydride in dichloromethane gave excellent yields of 1,2-bis(trifluoroacetoxy)thioethers 6. Mildly basic methanolysis of 2-alkyl-substituted 6 gave α-hydroxyaldehydes 11 as monomer-dimer mixtures; similar treatment of the 2-aryl analogues afforded aryl (hydroxymethyl) ketones 12. Compounds 11 underwent Wittig reactions with methoxycarbonylmethylenetriphenylphosphorane to give high yields of γ-hydroxy-α,β-unsaturated esters 13, predominantly as the E-isomers. β-Monosubstituted vinylic sulfoxides 1 possessing a β-aryl group, and β-disubstituted vinylic sulfoxides 3 reacted with trifluoromethanesulfonic anhydride-sodium acetate in acetic anhydride to give 2-(phenylsulfenyl) acylals 14. These gave 2-phenylsulfenyl aldehydes 15 upon basic methanolysis, and the corresponding primary alcohols 16 on reduction with sodium borohydride. Reaction of both geometric isomers of enantiomerically pure vinylic sulfoxide 1o with TFAA gave racemic 6o as a mixture of diastereomers. Reaction of optically pure (E)- and (Z)-1p with trifluoromethanesulfonic anhydride-sodium acetate in acetic anhydride gave acylal 19 in 10.5 and 23% e.e., respectively.
- Craig, Donald,Daniels, Kevin,MacKenzie, A. Roderick
-
p. 11263 - 11304
(2007/10/02)
-
- The reaction of 2-trimethylsilylethyl sulfoxides with sulfuryl chloride. A fragmentation route to sulfinyl chlorides
-
Sulfinyl chlorides were prepared in good to excellent yields by reacting aryl or alkyl 2-trimethylsilylethyl sulfoxides with SO2Cl2.
- Schwan,Dufault
-
p. 3973 - 3974
(2007/10/02)
-
- Convenient methods for the preparation of sulfur substituted allenecarboxylates
-
2-Sulfinyl- and 2-sulfonylallenecarboxylates, as new 1,1-diacceptor substituted allenes, were prepared starting from methyl 4-hydroxy-4-methyl-2-pentynoate by a [2,3]-sigmatropic rearrangement. The sulfoxides could be reduced to the corresponding allenyl sulfides. A 2(5H)-furanone derivative was prepared by a side-reaction.
- Conrads,Mattay
-
-
- Direct Conversion of Thiols to Sulfinyl Chlorides by Sulfuryl Chloride
-
Sulfinyl chlorides are prepared in quantitative yield by the reaction of thiols with sulfuryl chloride/acetic acid at low temperature.
- Youn, Joo-Hack,Herrmann, Rudolf
-
-
- Multinuclear NMR Study of Variously Substituted Sulphonamides and Sulphinamides
-
13C, 15N and 17O NMR chemical shifts, and also 1J(CH) and 1J(NH) values, have been determined for variously substituted sulphonamides and some sulphinamides, either neat or in acetone or dimethyl sulphoxide solution.The effect of benzene ring substitutens on the chemical shifts of nitrogen and oxygen nuclei is slight, but N-substitution changes the shielding of both nuclei.Generally, an N-methyl substituent shields an amide nitrogen and an N,Ndimethyl substituent gives further slight shielding.On the other hand, an N-phenyl substituent deshilds the nitrogen strongly, but the deshielding effect of an N,N-diphenyl substituent is markedly smaller.The sulphonyl oxygens are deshilded relative to the sulphinyl oxygens, and N-methyl and N,N-dimethyl substituents shild the oxygen nucleus.The effect of N-phenyl and N,N-diphenyl substituents on the shielding of the oxygen atoms of the sulphonyl group is slight.The direct 1J(CH) coupling constants are similar, but they are characteristic of different type of sulphur amides.The 1J(NH) values are of the same order of magnitude for sulphonamides and sulphinamides, but are clearly smaller for N-unsubstituted amides than for N-substituted compounds.KEY WORDS Sulphonamide Sulphinamide Multinuclear NMR
- Ruosteuso, P.,Haekkinen, A.-M.,Mattila, T.
-
p. 189 - 193
(2007/10/02)
-
- A SIMPLE AND EFFICIENT PREPARATION OF SULFINYL CHLORIDES FROM DISULFIDES AND SULFURYL CHLORIDE
-
Disulfides react with sulfuryl chloride in the presence of acetic acid to form the corresponding sulfinyl chlorides in nearly quantitative yield.
- Youn, Joo-Hack,Herrmann, Rudolf
-
p. 1493 - 1494
(2007/10/02)
-
- Chlorinolyses of Alkyl (or Aryl) Phtalimidomethyl Sulfides with Sulfuryl Chloride or Chlorine in the Presence and the Absence of Acetic Acid
-
Alkyl and aryl phtalimidomethyl sulfides give alkane- and arenesulfenyl chlorides on reaction with equimolar sulfuryl chloride or molecular chlorine in an aprotic solvent at room temperature, but give alkene- and arenesulfinyl chlorides on reaction with two molar equivalents of the same reagent in the presence of acetic anhydride under the same conditions.The utility of these reactions for the synthesis of organo sulfenyl chlorides and sulfinyl chlorides was confirmed.Keywords- chlorinolysis; oxidative cleavage; alkyl (or aryl) phtalimidomethyl sulfide; alkane (or arene) sulfinyl chloride; 2-chloro-alkyl sulfides; α,β-unsaturated sulfides
- Uchino, Makoto,Sekiya, Minoru
-
p. 126 - 133
(2007/10/02)
-