Reactions of polyfluorinated thietanes

Петров, В. А.; Marshall, William J.

doi:10.1016/j.jfluchem.2009.06.011

Cited by 13 publications

(15 citation statements)

References 33 publications

(48 reference statements)

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“…(1)). The KF catalyzed thietane synthesis was incorporated in a recently reported ''one-pot'' type synthesis of various 5-R-2-fluoro-3-trifluoromethyl-2,3-dihydrothiophenes [5].…”

Section: Resultsmentioning

confidence: 99%

“…For example, 2,2-bis(trifluoromethyl)-4-R-thietanes (R = -OR) were converted to fluorinated 1,2-dithiolanes [3]; a number of unsaturated products, were prepared as the result of ring opening processes [3,4], along with the corresponding S-oxides [5], and 5-R-2-fluoro-3-trifluoromethyl-2,3-dihydrothiophenes [5].…”

Section: Introductionmentioning

confidence: 99%

“…It is based on the reaction of, stable at ambient temperature, 2,2,4,4-tetrakis(trifluoromethyl)-1,3-dithietane (1, cyclic dimer of HFTA, prepared by reaction of sulfur and hexafluoropropene (HFP) in the presence of KF catalyst [7,8]) with methyl-or ethyl-vinyl ethers [3]. Recently we reported, a ''one-pot'' process for preparation of 5-alkoxy-2-fluoro-3-trifluoromethyldihydrothiophenes starting with sulfur, HFP and vinyl ether [5]. In course of that work we discovered an interesting effect of the catalyst on the reaction of sulfur, HFP and vinyl ethers, which is reported in this publication.…”

Section: Introductionmentioning

confidence: 99%

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Remarkable effect of metal fluoride catalyst on reaction of hexafluoropropene, sulfur and vinyl ethers. Convenient synthesis of 2,2-bis(trifluoromethyl)-4-R-thietanes, 3,3-bis(trifluoromethyl)-5-R-1,2-dithiolanes and 2,2-bis(trifluoromethyl)-4-R-1,3-dithiolanes

Петров¹,

Marshall²

2010

Journal of Fluorine Chemistry

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“…(1)). The KF catalyzed thietane synthesis was incorporated in a recently reported ''one-pot'' type synthesis of various 5-R-2-fluoro-3-trifluoromethyl-2,3-dihydrothiophenes [5].…”

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Remarkable effect of metal fluoride catalyst on reaction of hexafluoropropene, sulfur and vinyl ethers. Convenient synthesis of 2,2-bis(trifluoromethyl)-4-R-thietanes, 3,3-bis(trifluoromethyl)-5-R-1,2-dithiolanes and 2,2-bis(trifluoromethyl)-4-R-1,3-dithiolanes

Петров¹,

Marshall²

2010

Journal of Fluorine Chemistry

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“…Of the cis-and trans-diastereomeric mixture of thietanes, the cis isomer selectively reacted with the nitrenoid to form the intermediate (N-S Reaction of 4-substituted 2,2-bis(trifluoromethyl)thietanes with activated aluminum powder results in a highly selective ring-expansion process, producing the corresponding 2-substituted 5-fluoro-4-(trifluoromethyl)-2,3-dihydrothiophenes in 50-93% yields. Bi-and tricyclic thietane derivatives underwent similar ring expansions to afford bi-and tricyclic 2,3-dihydrothiophene derivatives, respectively [144] (Scheme 68).…”

Section: Synthesis Of Five-membered Heterocycles By Ring Expansion Ofmentioning

confidence: 99%

“…These unsaturated radicals further undergo a reduction into anions. Nucleophilic intramolecular attack of the sulfide anion on the positively charged carbon of the CF 2 group results in the formation of 2,3-dihydrothiophenes [144] (Scheme 69).…”

Section: Synthesis Of Five-membered Heterocycles By Ring Expansion Ofmentioning

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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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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Synthesis of Thietanes from Saturated Three‐membered Heterocycles

2020

Asian J Org Chem

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Thietanes are important structural motifs of some biological compounds and useful intermediates in organic synthesis. Various synthetic methods of thietanes have been developed recently with readily available saturated three‐membered heterocycles as starting materials or key intermediates. Both saturated three membered heterocycle‐2‐methyl halides and sulfonates and thiiranes are widely utilized materials. Both nucleophilic and electrophilic ring expansions of thiiranes are efficient methods for synthesis of thietanes. In this Focus Review, we have described various strategies for the synthesis of strained four‐membered thiaheterocyclic thietanes from readily available strained and saturated three‐membered heterocycles.

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Reactions of polyfluorinated thietanes

Cited by 13 publications

References 33 publications

Remarkable effect of metal fluoride catalyst on reaction of hexafluoropropene, sulfur and vinyl ethers. Convenient synthesis of 2,2-bis(trifluoromethyl)-4-R-thietanes, 3,3-bis(trifluoromethyl)-5-R-1,2-dithiolanes and 2,2-bis(trifluoromethyl)-4-R-1,3-dithiolanes

Remarkable effect of metal fluoride catalyst on reaction of hexafluoropropene, sulfur and vinyl ethers. Convenient synthesis of 2,2-bis(trifluoromethyl)-4-R-thietanes, 3,3-bis(trifluoromethyl)-5-R-1,2-dithiolanes and 2,2-bis(trifluoromethyl)-4-R-1,3-dithiolanes

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

Synthesis of Thietanes from Saturated Three‐membered Heterocycles

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