16192-08-8Relevant articles and documents
Metal-Free C-C Coupling of an Allenyl Sulfone with Picolyl Amides to Access Vinyl Sulfones via Pyridine-Initiated in Situ Generation of Sulfinate Anion
Omer, Humair M.,Liu, Peng,Brummond, Kay M.
, p. 7959 - 7975 (2020/07/15)
Vinyl sulfones are privileged motifs known for their biological activity and synthetic utility. Synthetic transformations to efficiently access high-value compounds with these motifs are desired and sought after. Herein, a new procedure is described to fo
Generation of 1,2-oxathiolium ions from (arysulfonyl)- and (arylsulfinyl)allenes in Br?nsted acids. NMR and DFT study of these cations and their reactions
Lozovskiy, Stanislav V.,Ivanov, Alexander Yu.,Khoroshilova, Olesya V.,Vasilyev, Aleksander V.
, p. 2897 - 2906 (2018/12/13)
In strong Br?nsted acids (CF3SO3H, FSO3H, D2SO4), (arysulfonyl)allenes (ArSO2-CR1=C=CR2R3) and (arylsulfinyl)allenes (ArSO-CR1=C=CR2R3) undergo cyclization into the corresponding stable 1,2-oxathiolium ions, which were studied by means of NMR and DFT calculations. Quenching of solutions of these cations with low nucleophilic media, aqueous HCl, leads to their deprotonation with a stereoselective formation of (arysulfonyl)butadienes (for instance, ArSO2-CR1=C-C(Me)=CH2, for R2 = R3 = Me, yields of 87-98%). Reactions of (arysulfonyl)allenes in the system TfOH (0.1 equiv)-HFIP (hexafluoropropan-2-ol) followed by hydrolysis give rise to allyl alcohols (ArSO2-CR1=CH-C(OH)R2R3, yields of 78-99%). Reflux of solutions of (arysulfonyl)allenes in the presence of TfOH (1 equiv) in 1,2-dichlorobenzene leads to the cyclization into thiochromene 1,1-diox-ides in high yields. Under the action of TfOH or AlX3 (X = Cl, Br) followed by hydrolysis of reaction mixtures, (arylsulfinyl)allenes give allyl alcohols (ArSO2-CR1=CH-C(OH)R2R3). Plausible reaction mechanisms have been proposed for all studied reactions.
Efficient synthesis of aliphatic sulfones by Mg mediated coupling reactions of sulfonyl chlorides and aliphatic halides
Fu, Ying,Xu, Qin-Shan,Li, Quan-Zhou,Du, Zhengyin,Wang, Ke-Hu,Huang, Danfeng,Hu, Yulai
, p. 2841 - 2845 (2017/04/03)
Sulfonyl chlorides were reduced to anhydrous sulfinate salts with magnesium under sonication. These sulfinates were alkylated to sulfones with alkyl chlorides in the presence of catalytic sodium iodide under sonication. A variety of aliphatic sulfones was efficiently prepared by this one-pot two-step procedure.
Silver-catalyzed rearrangement of propargylic sulfinates to allenic sulfones
Harmataa, Michael,Huanga, Chaofeng
experimental part, p. 972 - 974 (2009/05/27)
Treatment of propargylic sulfinate esters with 2 mol% of silver hexafluoroantimonate results in the rapid formation of allenic sulfones in essentially quantitative yield.
Additions of Organocopper Reagents and Heteroatom Nucleophiles to l-Phenylseleno-2-(p-toluenesulfonyl)ethyne. Preparation of Vinyl and Allenic Sulfones and Formation of Michael, Anti-Michael, and Rearrangement Products
Back, Thomas G.,Bethell, Richard J.,Parvez, Masood,Wehrli, Daniel
, p. 7908 - 7919 (2007/10/03)
l-Phenylseleno-2-(p-toluenesulfonyl)ethyne (4) was produced nearly quantitatively from p-(toluenesulfonyl)ethyne and benzeneselenenyl chloride. It undenvent stereo- and regioselective synadditions of organocopper reagents RCu(CN)Li to the β-position of th
Synthesis of thiophenes from allenyl sulfones involving α,β-unsaturated sulfines as intermediates
Linden, Johannes B. van der,Asten, Peter F. T. M. van,Braverman, Samuel,Zwanenburg, Binne
, p. 51 - 60 (2007/10/02)
The synthesis of thiophenes starting from allenyl sulfones, via intermediate formation of α,β-unsaturated sulfines, is described.The allenyl sulfones were synthesized by a -sigmatropic rearrangement of appropriately substituted prop-2-ynyl sulfinates
1-(Phenylseleno)-2-(p-toluenesulfonyl)ethyne. A Novel Acetylenic Sulfone That Undergoes Normal and Anti-Michael Nucleophilic Additions
Back, Thomas G.,Wehrli, Daniel
, p. 4737 - 4740 (2007/10/02)
1-(Phenylseleno)-2-(p-toluenesulfonyl)ethyne (3) was prepared from p-toluenesulfonylethyne and benzeneselenenyl chloride in the presence of triethylamine.It undergoes sequential conjugate addition and substitution of the selenium moiety with higher orded
Preparation of Allenic Sulfones and Allenes from the Selenosulfonation of Acetylenes
Back, Thomas G.,Krishna, M. Vijaya,Muralidharan, K. Raman
, p. 4146 - 4153 (2007/10/02)
β-(Phenylseleno)vinyl sulfones 2 are readily obtained from the free-radical selenosulfonation of acetylenes.Compounds 2 isomerize to allyl sulfones 4 under base-catalyzed conditions in nearly quantitative yield, with high stereoselectivity favoring the Z configuration.Allyl sulfones 4 afford generally high yields of allenic sulfones 1 when subjected to oxidation with m-chloroperbenzoic acid or tert-butyl hydroperoxide, followed by selenoxide syn-elimination.The sulfone-stabilized anion intermediates in the isomerizations of 2 to 4 can be alkylated, deuterated,or silylated in the α-position prior to oxidation, providing allenic sulfones with an additional α-substituent.In some cases, spontaneous elimination of the phenylseleno group occurred, producing the allenic sulfone without the need for an oxidation step.Desulfonylation of allyl sulfones 4f, 4c, and 25 with sodium amalgam afforded vinyl selenides that were converted to allenes in moderate to good yields by oxidation-elimination.The copper catalyzed coupling of allyl sulfones 4 with Grignard reagents comprises an alternative route to vinyl selenide precursors of allenes.These procedures permit the synthesis of various α- and γ-substituted allenic sulfones and allenes from acetylenes.
Homolytic Displacement at Carbon. Part 3. First Example of α-Attack on the Allenyl- and Prop-2-ynyl-cobaloximes
Gupta, B. Dass,Roy, Sujit
, p. 1377 - 1384 (2007/10/02)
Allenylcobaloxime reacts with substituted benzenesulphonyl chlorides in an inert atmosphere under irradiation with tungsten lamps to give good yields of allenyl sulphones.However, the same reactions carried out in Srinivasan's photoreactor using a 400 W medium-pressure mercury lamp or under thermal conditions give exclusively prop-2-ynyl sulphones, by regiospecific rearrangement, in good yields.The corresponding reactions of (3,3-disubstituted allenyl) cobaloximes afford 1,1-disubstituted prop-2-ynyl sulphones irrespective of the conditions used.Similarly, prop-2-ynyl sulphones are formed exclusively in the reactions of prop-2-ynylcobaloxime with organosulphonyl chlorides under thermal and photochemical conditions.The reactions are believed to take place through a chain mechanism in which cobaloxime(II), present adventitiously or formed by partial homolysis of the substrate cobaloxime, abstrscts a chlorine atom from the organosulphonyl chloride to give the organosulphonyl radical RSO2.Depending upon the reaction conditions and the nature of cobaloxime, RSO2 attacks the α- or the γ-carbon atom of the axial organic group of the cobaloxime, thereby displacing cobaloxime(II) and giving the observed organic product.
A GENERAL SYNTHESIS OF ALLENIC SULFONES FROM ACETYLENES USING SELENOSULFONATION
Back, Thomas G.,Krishna, M. Vijaya,Muralidharan, K. Raman
, p. 1737 - 1740 (2007/10/02)
Terminal acetylenes were converted to 1- and 3-substituted allenic sulfones via selenosulfonation, deprotonation, alkylation and selenoxide elimination.
