- A SIMPLE AND EFFICIENT PREPARATION OF SULFINYL CHLORIDES FROM DISULFIDES AND SULFURYL CHLORIDE
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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
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Read Online
- Non-expensive, open-flask and selective catalytic systems for the synthesis of sulfinate esters and thiosulfonates
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Two simple and efficient methods for the synthesis of sulfinate esters and thiosulfonates from sodium salts of sulfinic acids are described. Different alcohols were converted into the corresponding sulfinate esters in good yields and purity in an open flask. By the adjustment of the reaction conditions thiosulfonates could also be obtained in a very short reaction time.
- Tranquilino, Arisson,Andrade, Silvia R.C.P.,da Silva, Ana Paula M.,Menezes, Paulo H.,Oliveira, Roberta A.
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Read Online
- Direct Conversion of Thiols to Sulfinyl Chlorides by Sulfuryl Chloride
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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
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Read Online
- Improved Preparation of Optically Active Methyl p-Tolyl Sulfoxide
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An improved large scale procedure for the preparation of optically pure methyl p-tolyl sulfoxide is described as well as a large scale preparation of optically pure (-) menthyl (S)-p-tolylsulfinate
- Solladie, Guy,Hutt, Jean,Girardin, Andre
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Read Online
- Efficient diastereoselective intermolecular rhodium-catalyzed C-H amination
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(Chemical Equation Presented) Successful matchmaking: The combination of a chiral nitrene precursor with a chiral rhodium(II) catalyst is the key factor that allows efficient intermolecular regioselective C-H amination. Good-to-excellent yields and excellent diastereoselectivities can be obtained with a stoichiometric amount of the C-H bond containing substrate. nttl = N-1,8-naphthoyl-tert-leucine.
- Liang, Chungen,Robert-Peillard, Fabien,Fruit, Corinne,Mueller, Paul,Dodd, Robert H.,Dauban, Philippe
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Read Online
- Visible Light-Promoted Synthesis of β-Keto Sulfoximines from N-Tosyl-Protected Sulfoximidoyl Chlorides
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Under visible light, N-tosyl-protected sulfoximidoyl chlorides react with aryl alkynes to give β-keto sulfoximines. The reaction is characterized by a high functional group tolerance and good yields. It can be improved by the presence of a ruthenium photo
- Shi, Peng,Tu, Yongliang,Wang, Chenyang,Ma, Ding,Bolm, Carsten
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p. 3817 - 3824
(2022/02/05)
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- Regio- and Stereoselective Chloro Sulfoximidations of Terminal Aryl Alkynes Enabled by Copper Catalysis and Visible Light
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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
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supporting information
p. 2552 - 2556
(2021/03/19)
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- Exploiting Configurational Lability in Aza-Sulfur Compounds for the Organocatalytic Enantioselective Synthesis of Sulfonimidamides
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Methods for establishing the absolute configuration of sulfur-stereogenic aza-sulfur derivatives are scarce, often relying on cumbersome protocols and a limited pool of enantioenriched starting materials. We have addressed this by exploiting, for the first time, a feature of sulfonimidamides in which it is possible for tautomeric structures to also be enantiomeric. Such sulfonimidamides can readily generate prochiral ions, which we have exploited in an enantioselective alkylation process. Selectivity is achieved using a readily prepared bis-quaternized phase-transfer catalyst. The overall process establishes the capability of configurationally labile aza-sulfur species to be used in asymmetric catalysis.
- Dewez, Damien F.,Hall, Adrian,Martínez Lamenca, Carolina,Tilby, Michael J.,Willis, Michael C.
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supporting information
p. 25680 - 25687
(2021/11/09)
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- Direct conversion of sulfinamides to thiosulfonates without the use of additional redox agents under metal-free conditions
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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
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supporting information
p. 9291 - 9298
(2021/11/13)
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- Sulfur(IV)-Mediated Unsymmetrical Heterocycle Cross-Couplings
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Despite the tremendous utilities of metal-mediated cross-couplings in modern organic chemistry, coupling reactions involving nitrogenous heteroarenes remain a challenging undertaking – coordination of Lewis basic atoms into metal centers often necessitate elevated temperature, high catalyst loading, etc. Herein, we report a sulfur (IV) mediated cross-coupling amendable for the efficient synthesis of heteroaromatic substrates. Addition of heteroaryl nucleophiles to a simple, readily-accessible alkyl sulfinyl (IV) chloride allows formation of a trigonal bipyramidal sulfurane intermediate. Reductive elimination therefrom provides bis-heteroaryl products in a practical and efficient fashion.
- Zhou, Min,Tsien, Jet,Qin, Tian
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supporting information
p. 7372 - 7376
(2020/04/09)
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- N-Trifluoromethylthiolated Sulfonimidamides and Sulfoximines: Anti-microbial, Anti-mycobacterial, and Cytotoxic Activity
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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
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supporting information
p. 1457 - 1461
(2019/10/11)
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- Preparation method of chiral optical pure p-toluenesulfinamide
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The invention discloses a preparation method of a chiral optical pure p-toluenesulfinamide. The method includes: subjecting sodium p-tolylsulfinate and an acyl chlorination reagent to acyl chlorination to obtain p-toluene sulfinyl chloride, then reacting
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Paragraph 0014; 0041-0046
(2018/09/13)
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- Method for synthesizing chiral optical pure para-toluene sulfenamide
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The invention discloses a method for synthesizing chiral optical pure para-toluene sulfonamide. The method comprises the following steps: ensuring that para-toluene sulfinic acid sodium salt and an acylating chlorination reagent react with each other, so
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Paragraph 0040; 0041; 0042; 0043; 0044; 0045
(2018/09/21)
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- Preparation method of chiral optical pure p-toluene sulfamide
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The invention discloses a preparation method of chiral optical pure p-toluene sulfamide. The preparation method comprises the following steps: performing acylating chlorination by using sodium p-tolylsulfinate and an acylating chlorination reagent to obta
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Paragraph 0014; 0040; 0041; 0042
(2018/10/19)
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- Access towards enantiopure α,α-difluoromethyl alcohols by means of sulfoxides as traceless chiral auxiliaries
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A new methodology to access enantiopure α,α-difluoromethyl alcohols is hereby being described. The strategy relies on the use of an enantiopure aryl α,α-difluoromethyl sulfoxide employed as chiral and removable auxiliary for the stereoselective difluoromethylation of carbonyl derivatives. The obtained α,α-difluoro-β-hydroxysulfoxides displayed unprecedented diastereomeric ratios.
- Batisse, Chloé,Panossian, Armen,Hanquet, Gilles,Leroux, Frédéric R.
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supporting information
p. 10423 - 10426
(2018/09/21)
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- NOVEL SUBSTITUTED SULFOXIMINE COMPOUNDS
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The present invention relates to novel heterocyclic compounds of the general formula (I) their pharmaceutically acceptable salts, pharmaceutically acceptable solvates, enantiomers, diastereomers and polymorphs. The invention also relates to processes for the preparation of the compounds of invention, pharmaceutical compositions containing the compounds and their use as the compounds of the invention belong to the family of NOD-like receptor family (NLR) protein NLRP3 modulators. The present invention thus relates to novel NLRP3 modulators as well as to the use of the novel inhibitor compounds in the treatment of diseases or conditions as well as treatment of disease states mediated by NLRP3 as well as treatment of diseases or conditions in which interleukin 1β activity and interleukin-18 (IL-18) is implicated.
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Page/Page column 16; 17
(2019/01/06)
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- Preparation and reactions of enantiomerically pure α-functionalized grignard reagents
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A strategy for the generation of enantiomerically pure α- functionalized chiral Grignard reagents is presented. The approach involves the synthesis of α-alkoxy and α-amino sulfoxides in ≥99:1 dr and ≥99:1 er via asymmetric deprotonation (s-BuLi/chiral diamine) and trapping with Andersen's sulfinate (menthol derived). Subsequent sulfoxide → Mg exchange (room temperature, 1 min) and electrophilic trapping delivers a range of enantiomerically pure α-alkoxy and α-amino substituted products. Using this approach, either enantiomer of products can be accessed in 99:1 er from asymmetric deprotonation protocols without the use of (-)-sparteine as the chiral ligand. Two additional discoveries are noteworthy: (i) for the deprotonation and trapping with Andersen's sulfinate, there is a lack of stereospecificity at sulfur due to attack of a lithiated intermediate onto the α-alkoxy and α-amino sulfoxides as they form, and (ii) the α-alkoxy-substituted Grignard reagent is configurationally stable at room temperature for 30 min.
- Rayner, Peter J.,O'Brien, Peter,Horan, Richard A. J.
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supporting information
p. 8071 - 8077
(2013/07/11)
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- Asymmetric Synthesis of amines through rhodium-catalyzed C-H amination with sulfonimidoylnitrenes
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An efficient asymmetric C-H amination of benzylic and allylic substrates, as well as of adamantane derivatives, through catalytic C-H insertion of a chiral nitrene is reported. The reaction involves a chiral rhodium(II) complex, an iodine(III) oxidant, an
- Darses, Benjamin,Jarvis, Amandag.,Mafroud, Abdel-Kader,Estenne-Bouhtou, Genevieve,Dargazanli, Gihad,Dauban, Philippe
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p. 2079 - 2087
(2013/08/23)
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- Atropodiastereoselective C-H olefination of biphenyl p-tolyl sulfoxides with acrylates
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A stereoselective method for the synthesis of axially chiral biaryl scaffolds by C-H bond functionalization was accomplished using chiral sulfoxide both as the directing group enabling the regioselective activation of a C-H bond and as the chiral auxiliary generating an asymmetric environment in the coordination sphere of the metal complex. We have demonstrated the directing ability of the p-tolylsulfinyl group in promoting the Pd(II)-catalyzed C-H olefination of biphenyls.
- Wesch, Thomas,Leroux, Frederic R.,Colobert, Franoise
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supporting information
p. 2139 - 2144
(2013/10/01)
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- Synthesis of bis(4-methylphenylsulfonimidoyl)methane - The first free' geminal bis(sulfoximine)
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The synthesis of the first free' geminal bis(sulfoximine) bis(4-methylphenylsulfonimidoyl)methane is described. Herein we present two different synthetic routes leading either to the racemate or the enantiomerically pure compound. This representative of a new substance class can be regarded as a chiral analogue of the bis(iminophosphorane)s which are used as ligands in rare-earth-metal-catalyzed hydroamination reactions. Georg Thieme Verlag Stuttgart · New York.
- Reggelin, Michael,Mehler, Christian,Kaiser, Janphilipp
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supporting information; experimental part
p. 1095 - 1098
(2012/06/04)
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- Visible light-induced 3-sulfenylation of N-methylindoles with arylsulfonyl chlorides
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The synthesis of 1-methyl-3-(arylthio)-1H-indoles has been achieved by the photoredox reaction of N-methylindoles with readily available arylsulfonyl chlorides in moderate yields.
- Chen, Min,Huang, Zhi-Tang,Zheng, Qi-Yu
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supporting information
p. 11686 - 11688,3
(2012/12/12)
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- 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
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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
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experimental part
p. 387 - 393
(2011/06/11)
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- Synthesis of CF3-substituted sulfoximines from sulfonimidoyl fluorides
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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
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supporting information; experimental part
p. 768 - 771
(2011/04/24)
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- Sulfinamides as highly effective amine protecting groups and their use in the conversion of Amino alcohols into morpholines
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1,2-Amino alcohols have been converted into morpholines by using sulfinamides as temporary protecting/activating groups on the amine. We have developed a procedure for the selective synthesis of monoprotected N-sulfinyl amino alcohols through a double sul
- Fritz, Sven P.,Mumtaz, Amara,Yar, Muhammad,McGarrigle, Eoghan M.,Aggarwal, Varinder K.
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experimental part
p. 3156 - 3164
(2011/06/28)
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- Synthesis of enantiopure sulfonimidamides and elucidation of their absolute configuration by comparison of measured and calculated CD spectra and X-ray crystal structure determination
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Straightforward syntheses of enantiopure N-benzoyl- and N-tert-butyloxycarbonyl-protected sulfonimidamides, which can be used as building blocks in newly designed catalysts, are presented. Key synthetic step is a dynamic resolution of a racemic sulfinic acid sodium salt. All subsequent transformations proceed stereospecifically. The absolute configurations at the sulfur atoms of both sulfonimidamides were determined by comparison of measured and calculated CD spectra. An X-ray crystal structure determination of a sulfonimidoylguanidine derivative confirmed this result.
- Worch, Christin,Atodiresei, Iuliana,Raabe, Gerhard,Bolm, Carsten
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scheme or table
p. 677 - 683
(2010/06/19)
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- NEW COMPOUNDS FOR THE TREATMENT OF CANCER
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The invention provides a method of preparing the stereoisomers of 1,11-diamino-6-aza- undecane-2,4,8,10-tetraol.
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Page/Page column 19-20
(2009/12/28)
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- Intramolecular homolytic substitution of sulfinates and sulfinamides
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A general and efficient method for the synthesis of cyclic sulfi-nates and sulfinamides based on intra-molecular homolytic substitution (SHi) at the sulfur atom by aryl or alkyl radi-cals is described. Both alkyl and benzo-fused compounds can be accessed di-rectly from easily prepared acyclic pre-cursors. Enantiomerically enriched sulfur-based heterocycles were formed through an SHi process with inversion of configuration at the sulfur atom. Cyclization of prochiral radicals proceeded with varying stereochemical outcomes, depending on the size of the incoming radical. 2-Pyridyl and 2-qui-nolyl radicals led to biaryl compounds, which result from attack onto the ortho position of the arylsulfinate rather than a thiophilic substitution.
- Coulomb, Julien,Certal, Victor,Larraufie, Marie-Helene,Ollivier, Cyril,Corbet, Jean-Pierre,Mignani, Gerard,Fensterbank, Louis,Lacote, Emmanuel,Malacria, Max
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supporting information; experimental part
p. 10225 - 10232
(2010/04/05)
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- Toward a synthetically useful stereoselective C-H amination of hydrocarbons
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Reaction between a sulfur(VI) compound and an iodine(III) oxidant in the presence of a catalytic quantity (≤3 mol %) of a rhodium(II) catalyst leads to the formation of a chiral metallanitrene of unprecedented reactivity. The latter allows intermolecular C-H amination to proceed in very high yields up to 92% and excellent diastereoselectivities up to 99% with C-H bond containing starting materials as the limiting component. The scope of this C-H functionalization includes benzylic and allylic substrates as well as alkanes. Secondary positions react preferentially, but insertion into activated primary C-H bonds or sterically accessible tertiary sites is also possible. Cooperative effects between the nitrene precursor and the chiral catalyst at the origin of these good results have also been applied to kinetic resolution of racemic sulfonimidamide. This methodology paves the way to the use of Csp3-H bonds as synthetic precursors for the introduction of a nitrogen functionality into selected positions.
- Liang, Chungen,Collet, Florence,Robert-Peillard, Fabien,Mueller, Paul,Dodd, Robert H.,Dauban, Philippe
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p. 343 - 350
(2008/10/09)
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- N-phosphino-p-tolylsulfinamide ligands: Synthesis, stability, and application to the intermolecular Pauson-Khand reaction
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(Chemical Equation Presented) Here we synthesized a family of racemic and optically pure N-phosphino-p-tolylsulfinamide (PNSO) ligands. Their stability and coordination behavior toward dicobalt-alkyne complexes was evaluated. Selectivities of up to 3:1 we
- Reves, Marc,Achard, Thierry,Sola, Jordi,Riera, Antoni,Verdaguer, Xavier
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supporting information; experimental part
p. 7080 - 7087
(2009/05/09)
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- Reagent-controlled asymmetric homologation of boronic esters by enantioenriched main-group chiral carbenoids
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Putative enantioenriched carbenoid species, (R)-1-chloro-2- phenylethylmagnesium chloride (9) and (S)-1-chloro-2-phenylethyllithium (26), generated in situ by sulfoxide ligand exchange from (-)-(Rs,R)-1- chloro-2-phenylethyl p-tolyl sulfoxide (8), effected the stereocontrolled homologation of boronic esters. sec-Alcohols derived from the product boronates by oxidation with basic hydrogen peroxide exhibited % ee closely approaching that of sulfoxide 8 in examples employing Li-carbenoid 26.
- Blakemore, Paul R.,Marsden, Stephen P.,Vater, Huw D.
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p. 773 - 776
(2007/10/03)
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- Formation of cyclic sulfinates and sulfinamides through homolytic substitution at the sulfur atom
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(Chemical Equation Presented) Ring road: Cyclic sulfinates and sulfinamides can be synthesized by homolytic substitution to give alkyl and benzofused families of compounds. The presence of an additional heteroatom in the ring allows the preparation of sulfur-based heterocycles that are useful synthetic intermediates (see scheme). The stereogenic sulfur atom transfers its chirality to prochiral radicals. TTMSS = tris(trimethylsilyl)silane, AIBN = azobisisobutyronitrile.
- Coulomb, Julien,Certal, Victor,Fensterbank, Louis,Lacote, Emmanuel,Malacria, Max
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p. 633 - 637
(2007/10/03)
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- Serial ligand catalysis: A highly selective allylic C-H oxidation
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We are reporting a mild, chemo-, and highly regioselective Pd(II)-catalyzed allylic oxidation of α-olefins to furnish branched allylic esters that proceeds via a novel serial ligand catalysis mechanism in which two different ligands (i.e., vinyl sulfoxide 2 and BQ) interact sequentially with the metal to promote distinct steps of the catalytic cycle (i.e., C-H cleavage and π-allyl functionalization, respectively). Copyright
- Chen, Mark S.,Prabagaran, Narayanasamy,Labenz, Nathan A.,White, M. Christina
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p. 6970 - 6971
(2007/10/03)
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- p-Tolylsulfinyl Amides: Reagents for Facile Electrophilic Functionalization of Olefins
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A variety of olefins were found to react with sulfinyl amides in the presence of POCl3 to give β-chlorosulfides and β-hydroxysulfides in good yields. In the absence of nucleophiles, p-tolylsulfinyl amides were found to react with olefins with the formation of allylsulfoxides.
- Krasnova, Larissa B.,Yudin, Andrei K.
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p. 2584 - 2587
(2007/10/03)
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- Sulfonimidamides: Efficient chiral iminoiodane precursors for diastereoselective copper-catalyzed aziridination of olefins
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(Chemical equation presented) N-(p-Toluenesulfonyl)-p- toluenesulfonimidamide reacts with iodosylbenzene to afford in situ a chiral iminoiodane. The latter gives, in the presence of a copper(I) catalyst, a nitrene that is very efficiently transferred unde
- Di Chenna, Pablo H.,Robert-Peillard, Fabien,Dauban, Philippe,Dodd, Robert H.
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p. 4503 - 4505
(2007/10/03)
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- Sulfoximine derivatives as MMP-inhibitors or antibiotics
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The invention relates to the use of a sulfonamidimide of the formula I, wherein R1, R2 and R3 have the meanings given in the specification; or a tautomer thereof; or a salt of said compound or tautomer where salt-forming groups are present;for the manufac
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- Oxidative fragmentations of 2-(trimethylsilyl)ethyl sulfoxides - Routes to alkane-, arene-, and highly substituted 1-alkenesulfinyl chlorides
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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
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p. 1643 - 1654
(2007/10/03)
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- FeCl3 as an efficient and new catalyst for the thia-Fries rearrangement of aryl sulfinates
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Aryl arenesulfinates rearrange to the corresponding arenesulfinyl phenols via a thia-Fries rearrangement on catalysis by anhydrous FeCl3 in dry dichloromethane at room temperature in good to excellent yields.
- Matloubi Moghaddam, Firouz,Dekamin, Mohammad G.,Ghaffarzadeh, Mohammad
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p. 8119 - 8121
(2007/10/03)
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- Convenient method for the preparation of aryl sulfinyl chlorides
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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
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p. 1573 - 1574
(2007/10/03)
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- One-pot and simple reaction for the synthesis of alkyl p-toluenesulfinate esters under solid-phase conditions
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A manipulatively one-pot and rapid method for the synthesis of alkyl p-toluenesultinate esters 1 from p-toluenesulfinic acid, supported thionyl chloride on silica gel and aliphatic alcohols in solid phase conditions is described.
- Hajipour,Mallakpour,Afrousheh
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- Chiral N-Acyl-tert-butanesulfinamides: The "Safety-Catch" Principle Applied to Diastereoselective Enolate Alkylations
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Diastereoselective enolate alkylation reactions of N-acylsulfmamides and conversion of the alkylation products to a variety of enantiopure products are reported. Several sulfinamides were prepared in solution followed by acylation to provide N-acylsulfmamides. The N-acylsulfinamides were then evaluated in diastereoselective enolate alkylation reactions. Of the sulfinamides evaluated, tert-butanesulfinamide provided the highest diastereoselectivity. To establish the potential utility of sulfinamides as versatile auxiliaries, methods were developed for (1) the racemization-free acylation of tert-butanesulfinamide to prepare optically pure N-acyl-tert-butanesulfinamides, (2) the diastereoselective C-alkylation of N-acyl-tert-butanesulfmamides, (3) the conversion of the N-acyl-tert-butanesulfmamides to the active ester equivalent by N-alkylation and S-oxidation, and (4) the cleavage of the N-alkyl-N-acyl-tert-butanesulfonamides to give chiral alcohol, ester, amide, and carboxylic acid target compounds. These studies provide the groundwork for the development of sulfinamides as dual chiral auxiliaries and linkers for the multistep solid-phase synthesis of enantioenriched compounds.
- Backes, Bradley J.,Dragoli, Dean R.,Ellman, Jonathan A.
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p. 5472 - 5478
(2007/10/03)
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- Preparation of racemic and enantiopure arenesulfonimidoyl azoles - New compounds chiral on sulfur
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The novel arenesulfonimidoyl imidazoles 7a-j and nitrotriazoles 9d-j were obtained in good yield from the corresponding arenesulfonimidoyl chlorides 6a-j. The reaction of optically pure sulfonimidoyl chlorides 6 with imidazole resulted in the first reported optically active arenesulfonimidoyl imidazoles 7 with high enantiomeric purities (ee up to >99%); the stereochemical course of the reaction (inversion or retention at sulfur) is shown to be strongly dependent on the aryl substituent. By contrast, the analogous reaction of optically pure compounds 6 with 3-nitro-1,2,4-triazole led to racemic arenesulfonimidoyl nitrotriazoles 9. Optically active compounds of this type, (S)-9f (ee 99%) and (R)-9f (ee 92%), were obtained by semi-preparative chiral HPLC. The optically active arenesulfonimidoyl imidazolium salt (RS,RC)-8j was prepared by diastereoselective methylation (de >90%) of the optically pure imidazole derivative (RS,RC)-7j.
- Kluge, Ralph,Hocke, Heiko,Schulz, Manfred,Schilke, Frank
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p. 179 - 206
(2007/10/03)
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- Sulfonimidamide analogs of oncolytic sulfonylureas
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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.
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p. 1018 - 1025
(2007/10/03)
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- Enantioselective synthesis of haminol-1, an alarm pheromone of a Mediterranean mollusc
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The first enantioselective synthesis of (-)-(R)-haminol-1 is described in this paper. The chiral part of the molecule was prepared by reduction of an optically active β-ketosulfoxide. The all-trans trienic part was stereoselectively synthesized via reductive elimination of a 1,6-dibenzoate-2,4-diene with sodium amalgam.
- Solladie, Guy,Somny, Frederic,Colobert, Francoise
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p. 801 - 810
(2007/10/03)
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- The 'Thio-Arbuzov' reaction of sulfenate esters with sulfenyl chlorides: Fate of the thiosulfinate product
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The further reaction of thiosulfinate esters (putative products of the 'Thio-Arbuzov' reaction of sulfenate esters with sulfenyl chlorides) with sulfenyl chlorides and sulfenate esters has been studied. In the former case, sulfinyl chlorides and disulfides are formed. In the latter case sulfinate esters and disulfides are obtained. Copyright (C) 1996 Elsevier Science Ltd.
- Brown, Charles,Evans, Graham R.
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p. 9101 - 9104
(2007/10/03)
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- Nitrosations with hydrazine derivatives: Synthesis of N4-arenesulfinylsemicarbazides and N5-arenesulfinyl-N1-aminobiuretes from arenesulfinylisocyanates and N,N-disubstituted hydrazines
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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
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p. 344 - 351
(2007/10/02)
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- Sulfinyl chlorides through the oxidative chlorination of sulfenyl derivatives with trimethylsilyl acetate/sulfuryl chloride system
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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
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p. 1207 - 1213
(2007/10/02)
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- The reaction of 2-trimethylsilylethyl sulfoxides with sulfuryl chloride. A fragmentation route to sulfinyl chlorides
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Sulfinyl chlorides were prepared in good to excellent yields by reacting aryl or alkyl 2-trimethylsilylethyl sulfoxides with SO2Cl2.
- Schwan,Dufault
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p. 3973 - 3974
(2007/10/02)
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