ChemInform Abstract: ADDITION OF SULFENE CHLORIDES TO UNSATURATED COMPOUNDS

Rasteikene, L. P.; Greichute, D. I.; Lin'kova, M. G.; Knunyants, I. L.

doi:10.1002/chin.197738081

“…Presumably, the reaction mechanism is analogous to that proposed previously for arenesulfenamides [20]; it includes coordination of Lewis acid (phosphoryl halide) at the sulfur atom, generation of electrophilic species (sulfonium salt) by replacement of one halogen atom at the phosphorus, electrophilic addition of this species at the double C=C bond, and nucleophilic attack by halide ion (abstracted from the phosphoryl halide) to give trans-1,2-halosulfenylation product (Scheme 4). Obviously, as in the arylsulfenylation reactions [23][24][25], compounds IXb-XIVb are thermodynamically controlled products (the a : b ratios given in Scheme 6 refer to the products immediately after isolation). Different regioselectivities were observed in the addition to alkyl-and arylethenes.…”

Section: I Iimentioning

confidence: 99%

New Method of Synthesis of β-Haloalkyl Alkynyl Sulfides: Reaction of Alkynesulfenamides with Olefins in the Presence of Phosphoryl Halides

Белоглазкина

¹

,

Belova

²

,

Dubinina

³

et al. 2005

Russ J Org Chem

4

0

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Reactions of alkynelsufenamides with olefins (such as cyclohexene, norbornene, 1-hexene, 1-octene, allylbenzene, and styrene) in the presence of phosphoryl halides (POCl 3 , POBr 3 ) afforded 70-95% of β-halo-substituted alkyl alkynyl sulfides. The reactions with cyclohexene and norbornene are characterized by trans stereoselectivity. Alkynylsulfenylation of terminal alkyl-and benzylacetylenes occurs in a regioselective fashion with predominant formation of the corresponding anti-Markownikoff adducts, while the addition to styrene yields halogen-containing sulfides according to the Markownikoff rule.

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“…To our knowledge, such data for reactions of sulfenyl chlorides with alkenes were obtained for the first time in [4][5][6][7].…”

mentioning

confidence: 99%

Unusual reaction of 3,6-dimethoxy-benzonorbornadiene with 2-chloro-sulfenyl-1-pyridine 1-oxide

Борисов

¹

,

Османов

²

,

Sokolov

³

et al. 2004

Chem Heterocycl Compd

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In reactions of 3,6-dimethoxybenzonorbornadiene (1) with sulfenyl chlorides, usually mixtures of 1,2-addition and Wagner-Meerwein rearrangement products are obtained, and the yield of rearrangement products is significantly increased in the presence of salt additives [1,2].We have found that the primary direction of the reaction of the unsaturated compound 1 with 2-chlorosulfenyl-1-pyridine 1-oxide (2) in methylene chloride at 20°C is polar exo-cis cycloaddition of the sulfenylating reagent at the multiple bond, with closure of the ring by the oxygen atom of the N-oxide group and formation of polycyclic system 3a in 45% yield. The other direction of the reaction, the Wagner-Meerwein rearrangement, leads to γ-chloro sulfide 4, the yield of which is 34%. Formation of exclusively the product of polar cycloaddition 3b (the perchlorate analog of salt 3a) in 82% yield occurs upon sulfenylation of compound 1 in nitromethane in the presence of lithium perchlorate. OMe MeO N SCl O N O S OMe MeO Cl O S N MeO OMe + 1 2 CH 2 Cl 2 3b Cl _ + 3a _ + 4 MeNO 2 LiClO 4 _ + +Thus even under conventional conditions, sulfenyl chloride 2 reacts with unsaturated compound 1 preferentially according to a [4 + + 2] cycloaddition scheme [3]. To our knowledge, such data for reactions of sulfenyl chlorides with alkenes were obtained for the first time in [4][5][6][7].

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“…

In reactions of 3,6-dimethoxybenzonorbornadiene (1) with sulfenyl chlorides, usually mixtures of 1,2-addition and Wagner-Meerwein rearrangement products are obtained, and the yield of rearrangement products is significantly increased in the presence of salt additives [1,2].

We have found that the primary direction of the reaction of the unsaturated compound 1 with 2-chlorosulfenyl-1-pyridine 1-oxide (2) in methylene chloride at 20°C is polar exo-cis cycloaddition of the sulfenylating reagent at the multiple bond, with closure of the ring by the oxygen atom of the N-oxide group and formation of polycyclic system 3a in 45% yield. To our knowledge, such data for reactions of sulfenyl chlorides with alkenes were obtained for the first time in [4][5][6][7].

Formation of exclusively the product of polar cycloaddition 3b (the perchlorate analog of salt 3a) in 82% yield occurs upon sulfenylation of compound 1 in nitromethane in the presence of lithium perchlorate.…”

mentioning

confidence: 99%

“…To our knowledge, such data for reactions of sulfenyl chlorides with alkenes were obtained for the first time in [4][5][6][7]. To our knowledge, such data for reactions of sulfenyl chlorides with alkenes were obtained for the first time in [4][5][6][7].…”

mentioning

confidence: 99%

Unusual reaction of 3,6-dimethoxy-benzonorbornadiene with 2-chloro-sulfenyl-1-pyridine 1-oxide

Борисов

¹

,

Османов²,

Sokolov³

et al. 2004

Chem Heterocycl Compd

0

View full text Add to dashboard Cite

In reactions of 3,6-dimethoxybenzonorbornadiene (1) with sulfenyl chlorides, usually mixtures of 1,2-addition and Wagner-Meerwein rearrangement products are obtained, and the yield of rearrangement products is significantly increased in the presence of salt additives [1,2].We have found that the primary direction of the reaction of the unsaturated compound 1 with 2-chlorosulfenyl-1-pyridine 1-oxide (2) in methylene chloride at 20°C is polar exo-cis cycloaddition of the sulfenylating reagent at the multiple bond, with closure of the ring by the oxygen atom of the N-oxide group and formation of polycyclic system 3a in 45% yield. The other direction of the reaction, the Wagner-Meerwein rearrangement, leads to γ-chloro sulfide 4, the yield of which is 34%. Formation of exclusively the product of polar cycloaddition 3b (the perchlorate analog of salt 3a) in 82% yield occurs upon sulfenylation of compound 1 in nitromethane in the presence of lithium perchlorate. OMe MeO N SCl O N O S OMe MeO Cl O S N MeO OMe + 1 2 CH 2 Cl 2 3b Cl _ + 3a _ + 4 MeNO 2 LiClO 4 _ + +Thus even under conventional conditions, sulfenyl chloride 2 reacts with unsaturated compound 1 preferentially according to a [4 + + 2] cycloaddition scheme [3]. To our knowledge, such data for reactions of sulfenyl chlorides with alkenes were obtained for the first time in [4][5][6][7].

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ChemInform Abstract: ADDITION OF SULFENE CHLORIDES TO UNSATURATED COMPOUNDS

Cited by 3 publications

References 0 publications

New Method of Synthesis of β-Haloalkyl Alkynyl Sulfides: Reaction of Alkynesulfenamides with Olefins in the Presence of Phosphoryl Halides

New Method of Synthesis of β-Haloalkyl Alkynyl Sulfides: Reaction of Alkynesulfenamides with Olefins in the Presence of Phosphoryl Halides

Unusual reaction of 3,6-dimethoxy-benzonorbornadiene with 2-chloro-sulfenyl-1-pyridine 1-oxide

Unusual reaction of 3,6-dimethoxy-benzonorbornadiene with 2-chloro-sulfenyl-1-pyridine 1-oxide

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