- The Diels-Alder Reaction of Furan and Phenylsulphonylpropadiene. The Simple Base Induced Rearrangement of 3-Methylene-2-endo-phenylsulphonyl-7-oxabicyclohept-5-ene
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The Diels-Alder reaction of furan and phenylsulphonylpropadiene gives predominantly the 7-oxabicycloheptene (1), whose hydrogenation products (3) and (4) provide a simple entry to the synthesis of substituted cyclohexenols.
- Guildford, Allen J.,Turner, Ralph W.
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- Direct Decarboxylative Allylation and Arylation of Aliphatic Carboxylic Acids Using Flavin-Mediated Photoredox Catalysis
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We describe herein a direct decarboxylative allylation of aliphatic carboxylic acids with allylsulfones using visible light and riboflavin tetraacetate (RFTA) as photocatalyst. The reaction proceeds at room temperature tolerating a wide range of functiona
- Ramirez, Nieves P.,Lana-Villarreal, Teresa,Gonzalez-Gomez, Jose C.
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supporting information
p. 1539 - 1550
(2019/08/07)
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- 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
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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.
- Lozovskiy, Stanislav V.,Ivanov, Alexander Yu.,Khoroshilova, Olesya V.,Vasilyev, Aleksander V.
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p. 2897 - 2906
(2018/12/13)
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- Sulfinate-Organocatalyzed (3+2) Annulation Reaction of Propargyl or Allenyl Sulfones with Activated Imines
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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
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supporting information
p. 5069 - 5073
(2018/09/14)
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- Sulfinate-Organocatalyzed (3+2) Annulation of Allenyl Sulfones with 1,1-Dicyano Olefins in the Presence of a Quaternary Ammonium Phase Transfer Agent
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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
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supporting information
p. 2696 - 2706
(2018/07/29)
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- Unique Reactivity of α-Substituted Electron-Deficient Allenes using Sulfinate Salts as Lewis Base Organocatalysts
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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
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supporting information
p. 96 - 106
(2017/01/14)
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- Catalyst-controlled divergence in cycloisomerisation reactions of N-propargyl-N-vinyl sulfonamides: Gold-catalysed synthesis of 2-sulfonylmethyl pyrroles and dihydropyridines
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Gold-catalysed, divergent synthesis of 2-sulfonylmethyl pyrroles and dihydropyridines from N-propargyl-N-vinyl sulfonamides has been achieved. Echavarren's gold(i) catalyst promoted the formation of pyrrole derivatives whereas the combination of PPh3AuCl and AgSbF6 afforded dihydropyridines. The aza-enyne precursors for the cycloisomerisation reaction were prepared by a base-mediated formal vinylic substitution reaction of 2-bromoallyl sulfones.
- Undeela, Sridhar,Thadkapally, Srinivas,Nanubolu, Jagadeesh Babu,Singarapu, Kiran Kumar,Menon, Rajeev S.
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supporting information
p. 13748 - 13751
(2015/09/07)
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- Base-Mediated Cyclocondensation of Salicylaldehydes and 2-Bromoallyl Sulfones for the Synthesis of 3-Sulfonylchromene Derivatives and Their Regioselective Friedel-Crafts Heteroarylation Reactions
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Cesium carbonate-mediated reaction of 2-hydroxybenzaldehydes and 2-bromoallyl sulfones afforded 2H- and 4H-chromenol derivatives endowed with a 3-arylsulfonyl group. 2-Bromoallyl sulfones functioned as synthetic equivalents of allenyl sulfones under these conditions. The 2H- and 4H-chromenol derivatives underwent regioselective Friedel-Crafts reactions with heteroarenes in the presence of p-toluenesulfonic acid to afford 4-heteroaryl-4H-chromene derivatives in excellent yields.
- Kumar, Anand,Thadkapally, Srinivas,Menon, Rajeev S.
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p. 11048 - 11056
(2015/11/18)
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- Highly regio- and stereoselective palladium(0)-catalyzed addition of organoboronic acids with 1,2-allenic sulfones, sulfoxides, or alkyl- or aryl-substituted allenes in the presence of acetic acid: An efficient synthesis of E-alkenes
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Two sets of reaction conditions were established to enable the palladium(0)-catalyzed addition of organoboronic acids with 1,2-allenic sulfones, sulfoxides, or alkyl- or aryl-substituted allenes in the presence of acetic acid. This reaction provides a new
- Guo, Hao,Ma, Shengming
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p. 2731 - 2745
(2008/03/13)
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- Improved synthesis of 2,3-dibromo-1-(phenylsulfonyl)-1-propene (DBP)
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A convenient preparation of 2,3-dibromo-1-(phenylsulfonyl)-1-propene (DBP, 1) is available through the one-pot propargylation and oxidation of thiophenol to give the propargyl sulfone 11, which is isomerized and brominated in another one-pot reaction. The
- VanZanten, Aaron,Mullaugh, Katherine,Harrington, Ryan,Kiefer, Adam,Carlson, David,Mastarone, Dan,Lipchik, Corey,Murphree, S. Shaun
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p. 2611 - 2613
(2007/10/03)
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- REACTION OF AROMATIC N-OXIDES WITH DIPOLAROPHILES. XVII. CYCLOADDITION BEHAVIOUR OF ALLENES TOWARD PYRIDINE N-OXIDES AND FORMATION OF AZETIDINE-TYPE CYCLOADDUCT
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3,5-Dimethylpyridine N-oxide was allowed to react with phenylsulfonylpropadiene in CHCl3 at room temperature to give a mixture of the 1:1 sigmatropic rearrangement product and the 1:2 azetidine-type cycloadduct.The structure of the azetidine-type cy
- Matsuoka, Toshikazu,Hasegawa, Tomoaki,Harano, Kazunobu,Hisano, Takuzo
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p. 179 - 188
(2007/10/02)
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- Homolytic Displacement at Carbon. Part 3. First Example of α-Attack on the Allenyl- and Prop-2-ynyl-cobaloximes
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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.
- Gupta, B. Dass,Roy, Sujit
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p. 1377 - 1384
(2007/10/02)
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- Studies on the Addition of Allyl Oxides to Sulfonylallenes. Preparation of Highly Substituted Allyl Vinyl Ethers for Carbanionic Claisen Rearrangements
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Thirty-five allyl vinyl ethers bearing an arylsulfonyl anion-stabilizing group have been prepared by addition of allylic alkoxides to (arylsulfonyl)allenes.The allyl vinyl ethers are produced as either β,γ-unsaturated or α,β-unsaturated sulfones depending upon the substitution pattern of the allene and the reaction conditions.A wide variety of substitution patterns are available by using this method.Factors that control the position and stereochemistry of the vinyl ether double bond are discussed.
- Denmark, Scott E.,Harmata, Michael A.,White, Kathleen S.
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p. 4031 - 4042
(2007/10/02)
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- HOMOLYTIC DISPLACEMENT AT CARBON: FIRST EXAMPLE OF α-ATTACK IN THE ALLENYL AND PROPARGYL COBALOXIMES
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The reactions of allenyl and propalgyl cobaloximes with organosulphonyl chlorides under anaerobic and photochemical conditions form sulphones by a novel homolytic attack at the α carbon to the metal.
- Gupta, B.D.,Roy, Sujit
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p. 4905 - 4908
(2007/10/02)
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- Free-Radical Chain Substitution Reactions (SH2') of Alkenyl-, Alkynyl-, and (Alkenyloxy)stannanes
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Free-radical chain substitution reactions of allyltributylstannane were observed with PhSSPh, PhCH2SSCH2Ph, PhSeSePh, PhSO2Cl, n-PrSO2Cl, or CCl3SO2Cl, where the attacking radicals leading to allylic rearrangement with displacement of Bu3Sn(radical) were PhS(radical), PhCH2S(radical), PhSe(radical), PhSO2(radical), n-PrSO2(radical), and CCl3(radical), respectively.Allylic rearrangement was also observed in the SH2' reaction of crotyltributylstannane with PhSSPh, PhCH2SSCH2Ph, PhSO2Cl, or n-PrSO2Cl.Propargyltriphenylstannane underwent SH2' substitution to form the allenic substitution products with PhSO2Cl, n-PrSO2Cl, CCl4, and CHCl3 while 2-butynyltriphenylstannane formed the 1,2-butadiene with PhSO2Cl or n-PrSO2Cl.Reaction of (1-cyclohexenyloxy)tributylstannane with CCl4 or BrCCl3 formed α-(trichloromethyl)cyclohexanone.With HCBr3 the initially formed α-(dibromomethyl)cyclohexanone readily underwent dehydrobromination to form α-(bromomethylene)cyclohexanone. tributylstannane formed α-(trichloromethyl)isobutyraldehyde with CCl4 or BrCCl3.Reaction with HCBr3 gave a mixture of α-(dibromomethyl)isobutyraldehyde and 1-(dibromomethyl)-2,2-dimethyloxirane.
- Russell, Glen A.,Herold, Lourdes Lucas
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p. 1037 - 1040
(2007/10/02)
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