Allyl Phenyl Sulfide Research Articles

Palladium-Catalyzed Highly Chemo- and Stereoselective Bisthiolation of Terminal Alkynes with Allyl Phenyl Sulfides via C-S Bond Cleavage.

A facile and general method for palladium-catalyzed stereoselective bisthiolation of terminal alkynes with allyl phenyl sulfides has been developed. The scope and versatility of the reaction have been demonstrated, and a broad range of substrates bearing electron-donating and -withdrawing groups on the aromatic rings were all compatible with this reaction, providing the desired (Z)-1,2-dithio-1-alkenes in moderate to good yields. Preliminary mechanistic studies demonstrated that the sulfur source of the desired products may be successively incorporated into alkynes via C-S bond cleavage of two molecules of allyl phenyl sulfides and ruled out the possibility of vinyl sulfides, alkynyl sulfides, and disulfide intermediates being involved in this reaction.

Thermal Transformations of Allyl Phenyl Sulfide: A Quantum-Chemical Study

The transformation routes of allyl phenyl sulfide are calculated within the density functional theory (B3PW91/6-31G** quantum chemical approximation). We found that the chair conformation is a transition state of the first stage (the conversion of allyl phenyl sulfide into 6-(prop-2-en-1-yl)cyclohex-2,4-dien-1-thione). The second stage involves the interaction between thione and either allyl phenyl sulfide and allyl thiophenol molecule or with a second thione molecule. The cyclization of allyl thiophenol implies the formation of methyl thiocumaran. The thermal isomerization of allyl phenyl sulfide to propenyl phenyl sulfide is improbable.

Mechanism of the C=C Bond’s Migration in Allyl Phenyl Sulfide during Catalysis by Methanesulfonic Acid

The mechanism of the C=C bond’s migration in allyl phenyl sulfide in the presence of methanesulfonic acid is analyzed by quantum chemistry using the density functional theory in the B3PW91/6-31G** approximation. The reaction proceeds through the formation of 1-(phenylthio)prop-2-ylium and 2-methyl-1-phenylthiiranium. The calculations show the possibility of the protonation of allyl phenyl sulfide and deprotonation of the resulting cation to phenyl propenyl sulfide. The possibility of the opening of the thiiranium cation under the action of methyl sulfonate to form a complex of phenyl propenyl sulfide with methanesulfonic acid is also shown. Comparison of the results of calculations with and without a solvent shows that the energy profile of the reaction (ΔG 298 0 , and ΔE tot ) is practically preserved.

Understanding the molecular mechanism of thio-Claisen rearrangement of allyl phenyl sulfide and allyl vinyl sulfide using bonding evolution theory coupled with NCI analysis

ABSTRACTA joint application of bonding evolution theory (BET) and non-covalent interaction (NCI) analysis provides a powerful tool to explain the molecular mechanism of organic reactions. Thio-Claisen rearrangements (TCR) of allyl phenyl sulfide and allyl vinyl sulfide have been studied energetically using the MPWB1K/6-311G(2d,d,p), M06-2x/6-311G(2d,d,p) and the complete basis set model chemistry CBS-QB3 to predict activation barriers and thermodynamic parameters. Loss of aromaticity within the benzene ring along the TCR of allyl phenyl sulfide leads to a higher activation barrier and its endergonicity (endothermicity) nature, while TCR of allyl vinyl sulfide is an exergonic (exothermic) rearrangement with lower activation barrier. The molecular mechanisms are described by using MPWB1K/6-311G(2d,d,p) wavefunctions and energy profiles. The TCR of allyl phenyl sulfide and allyl vinyl sulfide can be described by the sequence of catastrophes 6-[C†C]F[F†F†F]TS[C†C]C†-0 and 8-C†CC[F†F†F]TSFCC†-0, respectively, by the following chemical events: (a) homolytic bond breaking of C−S single bond and formation of pseudoradical centers on the atoms; (b) annihilation of the pseudoradical centers and reorganization in covalent bonds; (c) appearance of the pseudoradical centers on the terminal carbon atoms; (d) formation of new C−C single bond by the C-to-C coupling of pseudoradical centers when the TS of the reaction is reached and left behind. NCI isosurface appears in the region of broken C−S bond and forming C−C bond where the monosynaptic basins were localized.

ChemInform Abstract: Diversity‐Oriented Stereoselective Synthesis of β,γ‐Disubstituted tert‐Homoallylic Alcohols.

ChemInformVolume 46, Issue 29 Preparative Organic Chemistry ChemInform Abstract: Diversity-Oriented Stereoselective Synthesis of β,γ-Disubstituted tert-Homoallylic Alcohols. Takeshi Takeda, Takeshi Takeda Dep. Appl. Chem., Grad. Sch. Eng., Tokyo Univ. Agric. Technol., Koganei, Tokyo 184, JapanSearch for more papers by this authorSota Amarume, Sota Amarume Dep. Appl. Chem., Grad. Sch. Eng., Tokyo Univ. Agric. Technol., Koganei, Tokyo 184, JapanSearch for more papers by this authorIppei Sekioka, Ippei Sekioka Dep. Appl. Chem., Grad. Sch. Eng., Tokyo Univ. Agric. Technol., Koganei, Tokyo 184, JapanSearch for more papers by this authorAkira Tsubouchi, Akira Tsubouchi Dep. Appl. Chem., Grad. Sch. Eng., Tokyo Univ. Agric. Technol., Koganei, Tokyo 184, JapanSearch for more papers by this author Takeshi Takeda, Takeshi Takeda Dep. Appl. Chem., Grad. Sch. Eng., Tokyo Univ. Agric. Technol., Koganei, Tokyo 184, JapanSearch for more papers by this authorSota Amarume, Sota Amarume Dep. Appl. Chem., Grad. Sch. Eng., Tokyo Univ. Agric. Technol., Koganei, Tokyo 184, JapanSearch for more papers by this authorIppei Sekioka, Ippei Sekioka Dep. Appl. Chem., Grad. Sch. Eng., Tokyo Univ. Agric. Technol., Koganei, Tokyo 184, JapanSearch for more papers by this authorAkira Tsubouchi, Akira Tsubouchi Dep. Appl. Chem., Grad. Sch. Eng., Tokyo Univ. Agric. Technol., Koganei, Tokyo 184, JapanSearch for more papers by this author First published: 02 July 2015 https://doi.org/10.1002/chin.201529063Read the full textAboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinkedInRedditWechat No abstract is available for this article. Volume46, Issue29July, 2015 RelatedInformation

Diversity-oriented stereoselective synthesis of β,γ-disubstituted tert-homoallylic alcohols.

The successive treatment of β-(trimethylsilyl)allyl phenyl sulfides with titanocene(II)-1-butene complex and ketones produced tertiary γ-(trimethylsilyl)homoallylic alcohols with good anti-selectivity, which reacted with a variety of organic halides in the presence of copper(I) tert-butoxide to afford the cross-coupling products, γ-substituted homoallylic alcohols.

ChemInform Abstract: Highly Diastereoselective Construction of Acyclic Systems with Two Adjacent Quaternary Stereocenters by Allylation of Ketones.

AbstractUnsymmetrical ketones and allyltitanocenes generated by the desulfurizative titanation of γ,γ‐disubstituted allyl phenyl sulfides give the corresponding alcohols.

Highly Diastereoselective Construction of Acyclic Systems with Two Adjacent Quaternary Stereocenters by Allylation of Ketones

Unsymmetrical ketones and allyltitanocenes generated by the desulfurizative titanation of γ,γ-disubstituted allyl phenyl sulfides react under highly diastereoselective construction of adjacent quaternary stereocenters (see scheme; R(L) = large group, R(S) = small group). The title reaction is stereospecific: the anti- and syn-homoallylic alcohols are obtained by the reaction of E- and Z-allylic sulfides, respectively.

ChemInform Abstract: Regio‐ and Enantioselective Iridium‐Catalyzed Allylation of Thiophenol: Synthesis of Enantiopure Allyl Phenyl Sulfides.

AbstractA highly regio‐ and enantioselective reaction of allylic carbonates with sodium thiophenolate is realized under conditions A.

Synthesis of Enantiopure Allyl Phenyl Sulfides

Asymmetric transition-metal-­catalyzed allylic substitutions are powerful synthetic transformations for the preparation of chiral allylic substrates. Herein, an iridium-catalyzed enantioselective allylation protocol using sodium thio­phenoxide 1 as a nucleophile has been developed. The best selectivities could be achieved with the chiral monodentate phosphoramidite ligand L*(S,S,S a )-5 and CsF as an additive in dichloromethane.

Regio- and Enantioselective Iridium-Catalyzed Allylation of Thiophenol: Synthesis of Enantiopure Allyl Phenyl Sulfides

A highly regio- and enantioselective allylic alkylation of sodium thiophenoxide has been realized by [Ir(COD)Cl](2)/phosphoramidite along with CsF as an additive, producing highly enantioenriched allyl phenyl sulfide compounds with up to 99% ee.

ChemInform Abstract: Preparation of (Me3P)2Pd2(.mu±eta.3-C3H5)(μ-SPh) by Reaction of Pd(0) Complex with Allyl Phenyl Sulfide.

ChemInform Abstract: Preparation of (Me3P)2Pd2(.mu±eta.3-C3H5)(μ-SPh) by Reaction of Pd(0) Complex with Allyl Phenyl Sulfide.

ChemInform Abstract: Efficient Synthesis of Vinylcycloalkyl Phenyl Sulfides from DME - Activated NaNH2-Induced Intramolecular Dialkylation of Allyl Phenyl Sulfide.

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

ChemInform Abstract: Asymmetric Copper-Catalyzed [2,3]-Sigmatropic Rearrangements of Alkyl- and Aryl-Substituted Allyl Sulfides.

The asymmetric copper-catalyzed generation and subsequent [2,3]-sigmatropic rearrangement of sulfur ylides is strongly dependent on the structure of the starting allyl sulfide. A series of alkyl and aryl substituted allyl sulfides (2a−i) were reacted with ethyl diazoacetate in the presence of copper triflate (CuOTf) and a C2-symmetric bis-oxazoline ligand (5a−c). The degree of asymmetric induction ranged from 2.8% for allyl methyl sulfide (2a) to 60% for (1S,2S,5R)-(+)-allyl menthyl sulfide (2d). The enantioselectivity of the reactions was also dependent on the electronic nature of the sulfide; allyl phenyl sulfide (2e) gave a 14% ee, whereas allyl p-methoxyphenyl sulfide (2i) produced only an 8% ee. The stereochemistry of 2d and (1R,2S,5R)-(+)-allyl menthyl sulfide (7) was assigned on the basis of NMR spectroscopic experiments.

Remarkable activity of the isomerization catalyst [RuCp(PPh 3) 2](OTs) in O-allylation of phenol with allyl alcohol

It was surprisingly found that the highly active allyl alcohol redox isomerization catalyst [RuCp(PPh 3) 2](OTs) upon addition of a catalytic amount of a strong acid can change its catalytic action fully to the selective O-allylation of phenols with allyl alcohol. High turnover numbers (75,000 based on phenol; 200,000 based on allyl alcohol) are reached, and the catalyst is very stable in the presence of substrate. Addition of triphenylphosphine to the reaction mixture does not lead to further stabilization of the catalyst; instead, the free phosphine is rapidly allylated, thereby consuming the acid, which deactivates the catalytic system for allylation reactions. This catalyst with monodentate phosphine ligands is superior in both activity and selectivity to similar catalysts with bidentate phosphine ligands. Apart from phenols, also thiophenol can be efficiently allylated to form allyl phenyl sulfide.

Readily Prepared 3-Chloro-1-(phenylthio)propene, a Versatile Three-Carbon Annulating Agent

3-Chloro-1-(phenylthio)propene, simply generated by chlorination of commercial allyl phenyl sulfide, is a versatile 3-carbon annulating agent for ketones and phenols.

Thiomaleic Anhydride: A Convenient Building Block for the Synthesis of α-Substituted γ- and δ-Lactones through Free-Radical Addition, Nucleophilic Ring Opening, and Subsequent Thiocarboxylate Manipulation

Iodoalkyl tert-butyl carbonates and carbamates undergo clean free-radical addition to thiomaleic anhydride to give substituted thiosuccinic anhydrides in high yield on treatment with tris(trimethylsilyl)silane and a radical initiator. After removal of the tert-butyloxycarbonyl group, cyclization then affords lactones or lactams substituted in the alpha-position by a thiocarboxylic acid residue. This group is converted to amides through reaction with electron-deficient sulfonamides or to aldehydes and/or ketones by the reaction of derived thioesters with either thiophenol, an electron-deficient allyl phenyl sulfide, or phenylboronic acid.

Silica-bound decatungstates as heterogeneous catalysts for H 2O 2 activation in selective sulfide oxidation

Alkylammonium decatungstates were covalently anchored to silica gel, furnishing efficient and robust heterogeneous catalysts able to activate H 2O 2 in the selective oxidation of sulfide to sulfoxide. The organic–inorganic hybrid materials were fully characterized, particularly by spectroscopic experiments. Primary propylammonium decatungstate was the most active catalyst. The use of low amounts of the heterogeneous catalyst (0.1 mol%) with a slight excess of 30% H 2O 2 (1.15 equiv.) in a nonchlorinated solvent (methanol) makes this oxidation reaction an environmentally benign chemical process. Leaching and recycling experiments revealed that the supported catalyst is not only highly efficient but also robust, because it can be used six times without loss of activity. Furthermore, the immobilized catalyst can tolerate different types of reaction solvents. Finally, this procedure was successfully applied to various sulfides, including allyl phenyl sulfide and dibenzyl sulfide.

Nickel‐Catalyzed Thioallylation of Alkynes with Allyl Phenyl Sulfides.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract, please click on HTML or PDF.

Nickel-Catalyzed Thioallylation of Alkynes with Allyl Phenyl Sulfides

Allylic sulfides add to alkynes in the presence of nickel complexes efficiently to afford thio-1,4-dienes regio- and stereoselectively. Functional groups such as alkoxy, siloxy, hydroxy, carboalkoxy, chloro, and cyano groups are tolerated. A mechanism that involves a pi-allyl nickel intermediate is proposed on the basis of isolation of pi-allyl complexes and distribution of products in the reactions of alpha- or gamma-methylated allyl sulfide. [reaction: see text].