Untitled

Томашевский, А. А.; Соколов, В. В.; Потехин, А. А.

doi:10.1023/a:1025592320130

Cited by 16 publications

(10 citation statements)

References 5 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The ringopening products generated by attacking the hindered carbon atom in the thiirane ring should be an intramolecular nucleophilic cyclization to yield intermediates 1-thioniabicyclobutanes and subsequent ring opening by attacking the hindered bridgehead carbon atom in the 1-thioniabicyclobutanes. The assumption of the existence of 1-thioniabicyclobutane intermediates was further verified by use of 2-chlorodideuteriomethylthiirane as starting material in the ring expansion with sodium phenoxide [38] (Scheme 6).…”

Section: Synthesis Of Four-membered Heterocycles By Ringmentioning

confidence: 95%

“…Recently, two Russian research groups reinvestigated the reaction of sodium phenolate and different 2-(chloromethyl)thiiranes [38,39]. 2-(1-Chloroalkyl) thiiranes reacted with sodium phenolates at heating in water-alcohol mixtures, furnishing 3-phenoxythietanes, or 2-(phenoxymethyl)thiiranes and 3-phenoxythietanes (resulting from thiirane-thietane rearrangement) mixture.…”

Section: Synthesis Of Four-membered Heterocycles By Ringmentioning

confidence: 99%

“…3-Chloromethyl-2,2-dimethylthiirane was a special case for it afforded 2,2-dimethyl-3-phenoxythietane and 3-methyl-2-butenyl disulfide without any 2-(phenoxymethyl)thiirane derivatives even in anhydrous ethanol. Diastereomeric erythro-and threo-(1-chloroethyl)thiiranes reacted stereospecifically, giving trans-2-methyl-3-(phenoxymethyl)thiiranes or cis-2-methyl-3-phenoxythietanes, respectively [38] (Scheme 5). Specific features of these reactions indicated that the competition between formal chlorine substitution along "recyclization" mechanism or through thiirane-thietane rearrangement via 1-thioniabicyclobutanes existed in the reaction.…”

Section: Synthesis Of Four-membered Heterocycles By Ringmentioning

confidence: 99%

“…The results further reveal that Sander previously mentioned that "abnormal ring opening" should not exist. Tomashevskii et al further discussed the reaction mechanism on the basis of the above reactions [38,39]. The ringopening products generated by attacking the hindered carbon atom in the thiirane ring should be an intramolecular nucleophilic cyclization to yield intermediates 1-thioniabicyclobutanes and subsequent ring opening by attacking the hindered bridgehead carbon atom in the 1-thioniabicyclobutanes.…”

Section: Synthesis Of Four-membered Heterocycles By Ringmentioning

confidence: 99%

See 3 more Smart Citations

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

2015

Topics in Heterocyclic Chemistry

View full text Add to dashboard Cite

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.

show abstract

Section: Synthesis Of Four-membered Heterocycles By Ringmentioning

confidence: 95%

Section: Synthesis Of Four-membered Heterocycles By Ringmentioning

confidence: 99%

Section: Synthesis Of Four-membered Heterocycles By Ringmentioning

confidence: 99%

Section: Synthesis Of Four-membered Heterocycles By Ringmentioning

confidence: 99%

See 2 more Smart Citations

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

2015

Topics in Heterocyclic Chemistry

View full text Add to dashboard Cite

show abstract

“…The most often used substrates in this reaction are phenols [18,19] and carboxylic acids [20], which give 3-aryloxy-and 3-acyloxythietanes respectively as products. Thietan-3-ol can be obtained from (chloromethyl)thiirane by the action of sodium carbonate in aqueous ethanol [21].…”

Section: Thiirane-thietane Rearrangementmentioning

confidence: 99%

Methods for the synthesis of derivatives of 3-aminothietane (Review)

Butkevich

Соколов

Томашевский

et al. 2007

Chem Heterocycl Compd

Self Cite

View full text Add to dashboard Cite

show abstract

Synthesis of Thietanes from Saturated Three‐membered Heterocycles

2020

Asian J Org Chem

View full text Add to dashboard Cite

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.

show abstract

Untitled

Cited by 16 publications

References 5 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

Methods for the synthesis of derivatives of 3-aminothietane (Review)

Synthesis of Thietanes from Saturated Three‐membered Heterocycles

Contact Info

Product

Resources

About