Alkyl vinyl thioethers

Typical of these materials are the poly(vinyl thioethers), the poly(vinyl isocyanates), the poly(vinyl ureas) and the poly(alkyl vinyl ketones). Methyl isopropenyl ketone and certain vinylpyridine derivatives have been copolymerised with butadiene to give special purpose rubbers. 

Catalytic hydrogenation with platinum liberates the hydrocarbon from methylcobalamin (57) and from alkyl-Co-DMG complexes (161), but not from pentacyanides with primary alkyl, vinyl, or benzyl ligands, though the cr-allyl complex yields propylene (109). Sodium sand gives mixtures of hydrocarbons with the alkyl-Co-salen complexes (64). Dithioerythritol will liberate methane from a variety of methyl complexes [cobalamin, DMG, DMG-BF2, G, DPG, CHD, salen, and (DO)(DOH)pn] (156), as will 1,4-butanedithiol from the DMG complex (157), and certain unspecified thiols will reduce DMG complexes with substituted alkyl ligands (e.g., C0-CH2COOH ->CH3C00H) (163, 164). Reaction with thiols can also lead to the formation of thioethers (see Section C,3). 

The hydrothiolation of terminal alkyl alkynes with 96 (Fig. 2.17) proceeds with good degree of regio- and chemo-selectivity, especially with thiophenol and p-methoxy-thiophenol as substrates. Isomerisation to the internal alkenyl thiolates accounts for less than 9% of the thiolated products under the reaction conditions. In addition, further hydrothiolation of the vinyl thioether product is not observed. Typical conversions of 70-85% at 1 mol% loading at 80°C within 5 h are observed. Arylthiols substituted with electron-withdrawing groups afford lower conversions. 

In Entry 5, the carbanion-stabilizing ability of the sulfonyl group enables lithiation and is then reductively removed after alkylation. The reagent in Entry 6 is prepared by dilithiation of allyl hydrosulfide using n-bulyl lithium. After nucleophilic addition and S-alkylation, a masked aldehyde is present in the form of a vinyl thioether. Entry 7 uses the epoxidation of a vinyl silane to form a 7-hydroxy aldehyde masked as a cyclic acetal. Entries 8 and 9 use nucleophilic cuprate reagents to introduce alkyl groups containing aldehydes masked as acetals. 

Vinyllithiums of type 663 (R2 = R3 = H) reacted with primary alkyl bromides, carbonyl compounds, carbon dioxide, DMF, silyl chlorides, stannyl chlorides, disulfides and phenylselenyl bromide142,970-979. Scheme 173 shows the synthesis of dihydrojasmone 669 from the corresponding 1,4-diketone. a-(Phenylsulfanyl)vinyllithium 665, prepared from phenyl vinyl thioether, reacted with hexanal and the corresponding adduct 666 was transformed into its acetoacetate. This ester 667 underwent a Carrol reaction to produce the ketone 668, which was transformed into the cyclopentenone 669 by deprotection either... 

Metallation of the most simple vinyl ether H2C=CHOCH3 in the a-position has been carried out with Fbutyllithium in THF at low temperatures [81]. Ethene is deprotonated not at all by FBuLi or other strongly basic systems under the same conditions. Sec-butyllithium has been used to metallate alkyl vinyl sulfides H2C=CH—SR [82]. We found that both vinyl ethers and vinyl thioethers can be metallated with excellent results using the cheaper combination of rc-BuLi and fBuOK [9]. The cyclic vinyl ethers 2,3-dihydrofuran and 2,3-dihydropyran can be successfully metallated under the same conditions ... 

Use of the methylsulphinyl carbanion as base is recommended for the synthesis of ethers from alcohols and alkyl halides. The catalysed formation of dimethyl ether from hydrogen and carbon dioxide has been reported. Carey has described the use of the silicon-modified organolithium reagent (73) in the preparation of vinyl thioethers (Scheme 151). In order to extend the scope of this reaction to include vinyl ethers themselves, an attempt was made to metalate trimethylsilylmethyl ether use of n-buty 1-lithium resulted in nucleophilic attack on silicon, whereas t-butyl-lithium abstracted the wrong proton, as shown in Scheme 151. 

Molecular weights increased with conversion in the phenylvinyl alkyl ether-MA copolymerizations. Under comparable conditions, lower copolymer yields were obtained for the vinyl thioether-MA pairs. Yields and molecular weight, in both cases, were shown to be highest when equimolar amounts of... 

The most promising tools developed for this sort of analysis are active-site-directed irreversible inhibitors of DUBs. These inhibitors are ubiquitin or ubiquitin-like proteins chemically modified at the C-terminus by an electrophilic moiety such as a Michael acceptor or alkyl halide. The modified ubiquitin can be incubated with a purified DUB or a cell lysate containing DUB activity. Ubiquitin vinyl sul-fone (UbVS) is one such irreversible inhibitor because the vinyl sulfone moiety reacts with the active-site cysteine of the DUB, forming a thioether linkage. The covalent adduct is stable and can be detected in a variety of ways. Labeling of DUBs is specific, as only a DUB active-site cysteine will efficiently react with the vinyl sulfone moiety. 

Thioethers (sulfides) can be prepared by treatment of alkyl halides with salts of thiols (thiolate ions).7S2 R may be alkyl or aryl. As in 0-35, RX cannot be a tertiary halide, and sulfuric and sulfonic esters can be used instead of halides. As in the Williamson reaction (0-12), yields are improved by phase-transfer catalysis.753 Instead of RS ions, thiols themselves can be used, if the reaction is run in benzene in the presence of DBU (p. 1023).754 Neopentyl bromide was converted to Me3CCH2SPh in good yield by treatment with PhS in liquid NH3 at -33°C under the influence of light.755 This probably takes place by an SrnI mechanism (see p. 648). Vinylic sulfides can be prepared by treating vinylic bromides with PhS in the presence of a nickel complex,756 and with R3SnPh in the presence of Pd(PPh3)4.757 R can be tertiary if an alcohol is the substrate, e.g,758... 

Thiols add to alkenes under photochemical conditions to form thioethers, and the reaction can be done intramolecularly to give cyclic thioethers. Thiols also add to alkynes and with a palladium catalyst, vinyl sulfides can be formed. Thio-carbonates function as thiol surrogates, converting alkenes to alkyl thiol in the presence of TiCl4 and CuO. °... 

This hypothesis has been verified starting from (Z)-y-iodoallyl ethers [109], amines [107], and thioethers [107] (Scheme 7-95) that are easily accessible from a propargyl ether [110] or ethyl propiolate [111]. In each case, the heteroatom chelates the vinylmetal to form a rigid five-membered ring and the allyl moiety approaches the vinyl one with a diastereofacial selectivity anti to the alkyl group [112]. 

Sulfur ylides have been used to generate bicyclic macrolactams, as shown in Scheme 35. Argogel-bound thioacetic acid 130 was synthesized from thioacetic acid esters by alkylation with Argogel-Cl resin and subsequent basic hydrolysis of the ester (not shown in Scheme 35). Esterification with co-hydroxy vinyl ketone 131 gave intermediate 132. Alkylation with MeOTf activated the thioether and reaction of 133 with DBU in CH2CI2 at room temperature provided the macrocycle 134 containing an additional cyclopropyl unit in 52 % yield as the pure trans diastereoi-somer [51]. 

The preparation of vinyl sulfides (or thioethers) has been extended by X-ray or irradiated addition of thiols to acetylene, and Pd(0Ac)2 or Pd(PPh3)4 catalyzed addition of thiol or disulfide to alkynes. In addition, alkyl halides (e.g., ethyl bromide, n-butyl bromide, 5 c-butyl bromide, benzyl chloride, etc.) have been successfully converted into corresponding vinyl sulfide through a one-pot process addition of acetylene mediated by thiourea. 

The following reactions of olefins have also been studied formation of dialkyl adducts (517) from vinyl monomers and dienes with lithium metal and alkyl bromides in THF alkylsulphonium salts (518) from thioethers and protonated alkenes hydroformylation of styrene and a-methylstyrene in the presence of bis-(iV-a-methylbenzylsalicylaldiminato)cobalt(n) to give 2-phenylpropanal (optical purity 1.9%) and 3-phenylbutanal (optical purity 2.9%) various electron-rich olefins of the type (519) with primary amines... 

Reactions at acid centers to create 5 -2-(trimethylsilyl) ethanethiolesters are also common. Carboxylic 5-thiolesters are formed in high yield by the DCC/DMAP mediated coupling of 2-(trimethylsilyl)ethanethiol and carboxylic acids or by thiol substitution on a carboxylic acid chloride. 5 -2-(Tiimethylsilyl) ethyl p-toluenethiolsulfonate is formed by treating 2-(trimethyl-silyl)ethanethiol with tosyl bromide (eq 4). The product is a useful electrophile for carbon nucleophiles, allowing the introduction of the 2-(trimethylsilyl)ethylthio unit by an alternative mechanism. Independent of the thiol, aryl and alkyl 2-trimethylsilylethyl thioethers may be prepared by the radical addition of the appropriate arene- or aikanethiol to vinyl trimethyl-silane in a reaction comparable to that of eq l7 ... 

Poly(l,4-pentadiene-alt-MA), 343, 348, 586 Poly(phenanthrene-alt-MA), 376, 660 Poly(phenylacetylene), MA grafted, 471 Poly(phenylacetylene-co-MA), 335, 660 Poly(2-phenylallyl alcohol-alt-MA), 331, 660 Poly(4-phenyl-l-butene-alt-MA), 340, 341 Poly(/- 1-phenylethyl methacrylate-co-MA), optically active polymer, 383 Poly(/-1-phenylethyl vinyl ether-alt-MA), optically active polymer, 383 Poly(5-phenyl-l-pentene-alt-MA), 340, 341 Poly( l-phenyl-4-pentene- 1-one-alt-MA), 314 Poly(3-phenyl propene-l-alt-MA), 341 Poly(o-phenylstyrene-alt-MA), 373 Poly(2-phenylvinyl alkyl ethers-alt-MA), 318 Poly(2-phenylvinyl alkyl thioethers-alt-MA), 318 Poly(phenyl vinyl ether-alt-MA), 318, 394 Poly(phenyl-o-vinyl formal-alt-MA), 328 Poly(phenyl vinyl ketone-co-MA), physical properties, 290... 

By analogy with the catalytic allylic alkylation performed with C-nucleo-philes described in Section 7.2.2.3, Plietker et al. used benzyl mercaptan as an S-nucleophile toward an isobutyl carbonate in the presence of an NHC-Fe complex 9. Allylic thioethers were obtained in 82% yield as a mixture of two regioisomers [eqn (7.7)]. The same group also investigated the sulfonylation of allylic carbonates with a-sulfonyl succinimides as S-nucleop-hiles. In this case, a base-free catalytic system generated in situ by thermal release of the SIMes carbene from its chloroform adduct in the presence of [Bu4N][Fe(CO)3(NO)] was adopted. Addition of DBU to the reaction mixtures allowed the one-pot synthesis of vinyl sulfones through a tandem iron-catalysed allylic sulfonylation/amine-catalysed isomerisation process. Remarkably, base-induced decomposition of the iron catalyst was not observed. 

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