Catalytic Transformations of Thiiranes by the W(CO)<sub>5</sub> Grouping. A New Route to Cyclic Polydisulfides

Adams, Richard D.; Queisser, Joachim; Yamamoto, John H.

doi:10.1021/ja960460l

Cited by 37 publications

(34 citation statements)

References 23 publications

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“…The reaction can be considered as a synthetic route to six-membered sulfur-containing heterocyclic 5,6-dihydro-1,4-dithiins [121]. Thus, thiiranes reacted with dimethyl acetylenedicarboxylate under the catalysis of tungsten carbonyl complexes to afford dimethyl 5,6-dihydro-1,4-dithiin-2,3-dicarboxylates (Scheme 47).…”

Section: Synthesis Of Six-membered Heterocycles By Ring Expansion Of mentioning

confidence: 99%

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Synthesis of Four- to Seven-Membered Heterocycles by Ring Expansion: Ring Expansions of Thiiranes and Thietanes

2015

Topics in Heterocyclic Chemistry

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Thiiranes and thietanes are important intermediates in organic synthesis, just as their oxygen and nitrogen analogs (oxiranes and aziridines, and oxetanes and azetidines). They have been widely applied in the preparation of sulfur-containing compounds. Thiiranes undergo ring expansions to generate various four-, five-, six-, and seven-membered heterocyclic products, even larger heterocycles. Thietanes also undergo ring expansions to produce five-, six-, and seven-membered heterocyclic compounds, even larger heterocycles as well. The ring expansions include insertion, nucleophilic and electrophilic ring opening, and subsequent cyclization. The regioselectivities in nucleophilic ring-opening reactions of unsymmetrical thiiranes and thietanes are discussed. Generally, nucleophiles attack on the less substituted vicinal carbon atom to the sulfur in unsymmetrical thiiranes and thietanes, controlled by steric hindrance. In the presence of Lewis acids, the electronic effect significantly impacts the regioselectivity in ring-opening reactions. 2-Arylthiiranes and 2-alkenylthiiranes are attacked on their more substituted vicinal carbon atom with nucleophiles (the electronic effect control). For thietanes, electrophilic ring expansion is one of the major processes. Unsymmetrical thietanes undergo electrophilic ring expansion with carbenes and nitrenes through electrophilic attack and subsequent Stevens-type rearrangement, with the more substituted vicinal carbon shifting. Mechanisms on some of the most important ring expansions of thiiranes and thietanes are introduced.

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Section: Synthesis Of Six-membered Heterocycles By Ring Expansion Of mentioning

confidence: 99%

“…The reaction of an excess of thiirane with W(CO) 5 (NCMe) led to the formation of the cyclic polydisulfides (CH 2 CH 2 SS) n (n ¼ 2-5) plus ethylene catalytically [121,123]. The eight-membered heterocyclic product 1,2,5,6-tetrathiocane is the major product.…”

Section: Synthesis Of Eight-membered and Larger Heterocycles By Ring mentioning

confidence: 99%

Synthesis of Four- to Seven-Membered Heterocycles by Ring Expansion: Ring Expansions of Thiiranes and Thietanes

2015

Topics in Heterocyclic Chemistry

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“…A new easier approach to cyclic poly(aliphatic disulfide)s by catalytic transformation of thiiranes by (thiirane)W(CO) 5 complexes has been studied (121)(122)(123)(124). For this purpose, the new thiirane complexes such as W(CO) 5 (thiirane) (c1), W(CO) 5 (cis-dimethylthiirane) (c2), and W(CO) 5 (trans-dimethylthiirane) (c3) were prepared and characterized.…”

Section: Poly(disulfide)smentioning

confidence: 99%

Sulfur‐Containing Polymers

Kultys

2010

Encyclopedia of Polymer Science and Technology

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Sulfur-containing polymers, when considering their structure, make up a complex group of macromolecular compounds of varied and often remarkable features that determine their versatile applications.The presence of sulfur atoms in polymer structure, depending on the kind of functional group, can improve some important properties, such as mechanical, electrical, and optical, and then adhesion to metals, resistance to heat, chemicals, radiation, and bacteria, biocompatibility, and so on. These are their more important functional groups: sulfide -S-, polysulfide -S n -, sulfonyl -SO 2 -, sulfinyl -SO-, sulfo -SO 3 H, as well as some organic groups containing sulfur atoms, such as thioester -Sulfur-containing polymers can be used as high performance engineering plastics, chemically stable ion-exchange membranes in electromembrane processes, proton-conducting electrolytes, as well as optical, optoelectronic, and photochemical materials. Some polymers are employed in biomedical applications, for example, sulfopolymers as biomembranes and blood-compatible materials, and polysulfates and polysulfonates as antithrombotic or antiviral agents. The presence of sulfur, particularly in the form of disulfide bridges, plays an important role in biopolymers.The purpose of this review is mainly to present recent advances in the area of sulfur-containing polymers that may not yet have commercial applications. Nevertheless, older but still significant material has been included at the beginning of the discussion of each class. Poly(monosulfide)sPolymers containing a monosulfide linkage in both the main chain and the pendent group are the subject of many detailed studies. A few reviews of the synthesis and properties of all types of polymers have been published (1-4); like the one covering polymer with sulfur in the main chain that appeared in 1992 (3). Polysulfides with controlled and well-defined structures can be easily prepared. Nevertheless, the only commercial poly(monosulfide) is Ryton [Philips Petroleum Co., poly(thio-1,4-phenylene) more frequently referred to as poly(p-phenylene sulfide) or poly(phenylene sulfide) (PPS)].

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“…A new easier approach to cyclic poly(aliphatic disulfide)s by catalytic transformation of thiiranes by (thiirane)W(CO) 5 complexes has been studied (85,86). For this purpose, the new thiirane complexes such as W(CO) 5 (thiirane) (c1), W(CO) 5 (cis-dimethylthiirane) (c2), and W(CO) 5 (trans-dimethylthiirane) (c3) were prepared and characterized.…”

Section: Poly(disulfide)smentioning

confidence: 99%

“…Cyclic disulfides have been shown to exhibit a variety of antimicrobial properties (85,88). The compounds 1,2,5,6-tetrathiacyclooctane (29a) and 1,2,5,6,9,10hexathiacyclododecane (29b) were tested for antimicrobial activity, using a standard disk diffusion assay.…”

Section: Poly(disulfide)smentioning

confidence: 99%

Sulfur‐Containing Polymers

Kultys¹

2001

Encyclopedia of Polymer Science and Technology

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Vol. 4 SULFUR-CONTAINING POLYMERS 337Nevertheless, the only commercial poly(monosulfide) is Ryton [Philips Petroleum Co., poly(thio-1,4-phenylene) more frequently referred to as poly(p-phenylene sulfide) or poly(phenylene sulfide) (PPS)]. Much effort has been devoted to preparing aromatic compounds in view of their significance as reactive intermediates for the synthesis of high performance linear aromatic polymers by ring-opening polymerization (ROP) (5). In an attempt to develop a novel synthetic method for the preparation of high molecular weight poly(thioarylene)s, macrocyclic aromatic sulfides and disulfides have been intensively prepared (6-14). The coordination chemistry of macrocyclic polysulfides has also received considerable attention during the past years. The thiacrown ether polymer ligands can be used as ion-exchange resins, metal ion adsorbents, and polymeric phase-transfer catalysts (15,16). Molecular systems in which tetrathiafulvalene is incorporated into macrocycles with supplementary donor atoms are potential electroactive cation sensors (17). The π -conjugated polymers have been extensively studied because of their attractive electronic properties. SULFUR-CONTAINING POLYMERSVol. 4The novel partially crystalline polymer (3) with number-average molecular weight (M n ) of up to 5700 was prepared under various conditions by catalyzed self-condensation of 3-hydroxypropyl methoxycarbonylethyl sulfide (4) or 3-hydroxypropyl carboxyethyl sulfide (5) (22). The degree of crystallinity, melting temperature (T m ), T g , and temperature of initial decomposition (T d ) were 36-46%, 37-47 • C, −61 to −70 • C, and 164-260 • C, respectively. The monomers (4) and (5) were prepared by an addition of methyl 3-mercaptopropionate and 3-mercaptopropionic acid with allyl alcohol [107-18-6] catalyzed by AIBN [2,2 -azobis(2-methylpropionitrile), azobisisobutyronitrile, azodiisobutyrodinitrile, 2,2 -azobis(2-methylpropanenitrile), α,α -azodiisobutyronitrile, 2,2 -azobis(isobutyronitrile), 2,2 -dicyano-2,2 -azopropane, Porofor-57, 2,2 -dimethyl-2,2azodipropionitrile, 2,2(-azobis(2-methylpropionitrile))] [78-67-1].An addition of conjugate 1,4-benzenedithiol (A) to 1,4-divinylbenzene (1,4diethenylbenzene, p-divinylbenzene) (B) [105-06-6] was investigated in detail in the presence of the AIBN initiator in toluene at 75 • C (23). It was found that the polymerization proceeded without an induction period, to give a white polymer with a high molecular weight [weight-average molecular weight (M w ) = 110,000] in ∼90% yield for 2 h. In addition, it was confirmed by 1 H nmr, ir, and the sulfur contents that the polymer had an alternating structure of A and B units.The synthesis and radical addition behavior of optically active cysteinebased monomers with mercapto and olefin groups have also been studied (24). N-4-vinylbenzoyl-L-cysteine methyl ester polymerized satisfactorily to afford the corresponding polysulfide (with M n in the range of 7000-23,000) in good yields.A novel one-pot synthesis of sulfur-containing polymers incl...

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Catalytic Transformations of Thiiranes by the W(CO)₅ Grouping. A New Route to Cyclic Polydisulfides

Cited by 37 publications

References 23 publications

Synthesis of Four- to Seven-Membered Heterocycles by Ring Expansion: Ring Expansions of Thiiranes and Thietanes

Synthesis of Four- to Seven-Membered Heterocycles by Ring Expansion: Ring Expansions of Thiiranes and Thietanes

Sulfur‐Containing Polymers

Sulfur‐Containing Polymers

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Catalytic Transformations of Thiiranes by the W(CO)5 Grouping. A New Route to Cyclic Polydisulfides

Cited by 37 publications

References 23 publications

Synthesis of Four- to Seven-Membered Heterocycles by Ring Expansion: Ring Expansions of Thiiranes and Thietanes

Synthesis of Four- to Seven-Membered Heterocycles by Ring Expansion: Ring Expansions of Thiiranes and Thietanes

Sulfur‐Containing Polymers

Sulfur‐Containing Polymers

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Catalytic Transformations of Thiiranes by the W(CO)₅ Grouping. A New Route to Cyclic Polydisulfides