Novel Sulfur Transfer Reaction from 5H-Benzo[f]-1,2,3,4-tetrathiepin or 6H-Benzo[g]-1,2,3,4,5-pentathiocin to Olefins

Sato, Ryo; Satoh, S.; Saito, Mitsugu

doi:10.1246/cl.1990.139

Cited by 31 publications

(12 citation statements)

References 16 publications

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“…Although few reports have appeared on the existence of sulfur-transfer, as S 3 , [47][48][49]60 compared to S 2 , [50][51][52][53][54] the computational results here argue that S 3 dissociation provides the favored low-energy route to pentathiepin decomposition. Pathways B and C were optimized with the resulting species isolated at a fixed distance of 5.0 Å (Scheme 4).…”

Section: Resultsmentioning

confidence: 60%

“…It should be noted that pentathiepins may cleave S 2 in a mass spectrometer, but that this high-energy process provides little information regarding species relevant in biochemistry. 6,7,20 Interestingly, Sato et al 60 suggested a possible equilibrium between S 3 and S 2 + S X . Unfortunately, the computational data collected thus far cannot corroborate this suggestion since S 2 may be expected to attack S X and lead to a polysulfur species, which exhibits no particular bias toward S 3 cleavage.…”

Section: Resultsmentioning

confidence: 99%

“…Upon heating of 6Hbenzo[g]-1,2,3,4,5-pentathiocin (22) with norbornene (23) a S 3 -transfer reaction occurs giving exo-3,4,5-trithiatricyclo-[5.2.1.0 2,6 ]decane (24, Scheme 11A). 60 Ghosh and Bartlett 47 also suggested that S 3 transfer may occur via the unequal bondbreaking of endo-2-phenyl-exo-3,4,5-trithiatricyclo[5.2.1.0 2,6 ]decane (25) giving 24 and 2-phenyl norbornene (26) and in a bimolecular concerted process (Scheme 11B). 47 Our computational data predict that open-chain 12 is a candidate for loss of S 3 ; however, further insight on alternative fragmentation pathways was needed.…”

Section: Resultsmentioning

confidence: 99%

“…A challenging aspect of structure determination is the assignment of reactive intermediates, such as organic anions 57 and polysulfur species. 22,[58][59][60][61] Chair-Chair Interconversion. There are a number of experimental 25 and theoretical 14,[25][26][27] studies on chair-chair interconversions of pentathiepins (represented as Pathway E in Scheme 4).…”

Section: Resultsmentioning

confidence: 99%

“…A related sulfur-transfer reaction may shed light on the mechanism of pentathiepin decomposition. Upon heating of 6H-benzo[ g ]-1,2,3,4,5-pentathiocin ( 22 ) with norbornene ( 23 ) a S 3 -transfer reaction occurs giving exo -3,4,5-trithiatricyclo[5.2.1.0 2,6 ]decane ( 24 , Scheme A) . Ghosh and Bartlett 47 also suggested that S 3 transfer may occur via the unequal bond-breaking of endo -2-phenyl- exo -3,4,5-trithiatricyclo[5.2.1.0 2,6 ]decane ( 25 ) giving 24 and 2-phenyl norbornene ( 26 ) and in a bimolecular concerted process (Scheme B) .…”

Section: Resultsmentioning

confidence: 99%

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On the Origin of Cytotoxicity of the Natural Product Varacin. A Novel Example of a Pentathiepin Reaction That Provides Evidence for a Triatomic Sulfur Intermediate

Greer

2001

J. Am. Chem. Soc.

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A density functional theoretical study is presented, which implicates a novel S(3)-cleavage in the decomposition of a pentathiepin. This study predicts an interconversion between a pentathiepin and an open-chain polysulfur ion intermediate from which a key determinant in the chemistry then follows. Expulsion of diatomic sulfur, S(2), is unlikely from the unimolecular collapse of the open-chain polysulfur ion. Instead, S(3) can dissociate due to an unusually long and weak sulfur-sulfur (S4-S5) bond. A mechanistic picture now emerges which predicts that the novel S-S cleavage reaction and the unanticipated S(3) fragmentation are a result of delocalization of the negative charge within the remaining carbon-sulfur fragment. The computed results presented here reveal a new aspect to the chemistry of pentathiepins, that of S(3) unit transfer, which is proposed to have significance in the mechanism of cytotoxicity of the natural product varacin, 1.

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Section: Resultsmentioning

confidence: 60%

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

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On the Origin of Cytotoxicity of the Natural Product Varacin. A Novel Example of a Pentathiepin Reaction That Provides Evidence for a Triatomic Sulfur Intermediate

Greer

2001

J. Am. Chem. Soc.

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Sulfur: Organic PolysulfanesBased in part on the article Sulfur: Organic Polysulfanes by Ralf Steudel & Monika Kustos which appeared in theEncyclopedia of Inorganic Chemistry, First Edition.

Atwood¹,

Zaman²

2005

Encyclopedia of Inorganic Chemistry

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Organic polysulfanes are compounds of the type RS n R with n > 2. They may be chain‐like or cyclic. The organic residues (alkyl or aryl) are linked to the sulfur atoms via carbon atoms. In the literature these compounds are often termed as organic polysulfides, but the IUPAC recommended nomenclature is polysulfanes. Sulfur‐rich organic polysulfanes can be viewed as intermediates between organic and inorganic compounds. On one hand, they are characterized by organic substituents R, which terminate the sulfur chain or close this chain to form a ring. On the other hand, compounds with sulfur chains of three or more sulfur atoms are ‘inorganic’ enough to attract the interest of inorganic chemists who have contributed much to this area. Organic polysulfanes with up to 16 sulfur atoms in the molecules have so far been obtained as pure substances, but species with up to 35 sulfur atoms in a chain or ring have been prepared in mixtures. Organic polysulfanes play an important role not only in basic research and industry, they are also found as natural products in organisms and occur in the inanimate nature. The main importance of organic polysulfanes comes, however, from their role in the large scale industrial vulcanization of natural and synthetic rubber. In this article, the preparation, structure, modern analysis, basic reactions, natural occurrence, biological activity, and practical importance of organic polysulfanes with three or more neighboring sulfur atoms in a chain or ring have been presented.

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Sulfur: Organic Polysulfanes

Steudel

2005

Encyclopedia of Inorganic Chemistry

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Novel Sulfur Transfer Reaction from 5H-Benzo[f]-1,2,3,4-tetrathiepin or 6H-Benzo[g]-1,2,3,4,5-pentathiocin to Olefins

Abstract: Many olefins trapped active sulfur species generated from 5H-benzo[f]-1,2,3,4-tetrathiepin (BTTP) or 6H-benzo[g]-1,2,3,4,5-pentathiocin (BPTC) in DMSO to give [2+3], [4+2], or [6+3] cycloadducts.

Cited by 31 publications

References 16 publications

On the Origin of Cytotoxicity of the Natural Product Varacin. A Novel Example of a Pentathiepin Reaction That Provides Evidence for a Triatomic Sulfur Intermediate

On the Origin of Cytotoxicity of the Natural Product Varacin. A Novel Example of a Pentathiepin Reaction That Provides Evidence for a Triatomic Sulfur Intermediate

Sulfur: Organic PolysulfanesBased in part on the article Sulfur: Organic Polysulfanes by Ralf Steudel & Monika Kustos which appeared in theEncyclopedia of Inorganic Chemistry, First Edition.

Sulfur: Organic Polysulfanes

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