Isolation of a crystalline thiete and its ‘open’ isomer; Photoproducts of xanthenethione and bis(tert-butylthio)ethyne

Brouwer, A. C.; George, A. V. E.; Seykens, Don; Bos, H. J. T.

doi:10.1016/s0040-4039(01)85747-6

Cited by 22 publications

(4 citation statements)

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“… 13 − 15 Due to the lower tendency of sulfur to form double bonds, thietes are more stable than oxetes, 16 − 21 and a dynamic equilibrium between the “closed” thiete and “open” α,β-unsaturated thioketone form was observed with thioether substituents. 22 , 23 Given these differences between oxetes and thietes, we became curious to explore how the introduction of another heavy main group element would affect the stability of the four-membered ring species. Although numerous examples for heavy main group carbonyls R 2 E=O and thiocarbonyls R 2 E=S have been synthesized, 24 − 34 the reactivity with alkynes is little developed.…”

Section: Introductionmentioning

confidence: 99%

“…These reactions have been extensively utilized in synthetic chemistry . The carbonyl–alkyne metathesis proceeds via a four-membered oxete intermediate, which is usually directly transformed into the α,β-unsaturated ketone, − unless it is stabilized by strongly electron-withdrawing groups. − Due to the lower tendency of sulfur to form double bonds, thietes are more stable than oxetes, − and a dynamic equilibrium between the “closed” thiete and “open” α,β-unsaturated thioketone form was observed with thioether substituents. , Given these differences between oxetes and thietes, we became curious to explore how the introduction of another heavy main group element would affect the stability of the four-membered ring species. Although numerous examples for heavy main group carbonyls R 2 E=O and thiocarbonyls R 2 E=S have been synthesized, − the reactivity with alkynes is little developed.…”

Section: Introductionmentioning

confidence: 99%

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Thiophosphonium–Alkyne Cycloaddition Reactions: A Heavy Congener of the Carbonyl–Alkyne Metathesis

et al. 2021

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While the metathesis reaction between alkynes and thiocarbonyl compounds has been thoroughly studied, the reactivity of alkynes with isoelectronic main group R 2 E=S compounds is rarely reported and unknown for [R 2 P=S] + analogues. We show that thiophosphonium ions, which are the isoelectronic phosphorus congeners to thiocarbonyl compounds, undergo [2 + 2]-cycloaddition reactions with different alkynes to generate 1,2-thiaphosphete ions. The four-membered ring species are in an equilibrium state with the corresponding P=C–C=S heterodiene structure and thus undergo hetero-Diels–Alder reactions with acetonitrile. Heteroatom and substituent effects on the energy profile of the 1,2-thiaphosphete formation were elucidated by means of quantum chemical methods.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Thiophosphonium–Alkyne Cycloaddition Reactions: A Heavy Congener of the Carbonyl–Alkyne Metathesis

et al. 2021

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“…Generally, (2+2)-cycloaddition products are formed from triplet thiones. Also with acetylenes (2+2)photocycloaddition reactions are usually observed [4][5][6][7][8][9][10][11]. Only in a few cases (4+2)-cycloaddition products can be isolated [12,13] .…”

Section: Introductionmentioning

confidence: 99%

Cycloaddition Reactions of Substituted Allenes with Triplet Excited Aromatic Thiones: Product Formation and Reaction Mechanism

Kamphuis

Grootenhuis

Ruijter

et al. 1985

Israel Journal of Chemistry

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The reactivity of substituted allenes H2CCC(R)X towards three triplet aromatic thiones has been investigated. Product analysis reveal the formation of two (2+2)‐cycloaddition products the thietanes 3, 4 (E + Z) and occasionally of one (4+2)‐cycloaddition product, thiopyran derivative (Z)‐5, generally in high overall yields. Steady state measurements show that electron donating substituents in the allenic system enhance the overall reaction rate. There is little effect of solvent polarity on the reaction rate. The correlation between the relative reaction rates and the first adiabatic ionization energy of the substituted allenes is in accordance with the formation of an exciplex between the excited thione and that π‐bond of the allenic system which is conjugated with the substituent X. From this exciplex two isomeric allylic 1,4‐biradicals (Z)‐8 and (E)‐8 are probably formed. After inter‐system crossing, ring closure gives the thietanes 3, (E)‐4, (Z)‐4 and/or thiopyran derivative (Z)‐5. The ratio in which 3, (E)‐4, (Z)‐4 and (Z)‐5 are formed is explained by considering electronic and steric factors in the proposed reaction mechanism. Experiments with an optically active allene (+)‐PhC(H)CC(H)Me support the intermediacy of a non‐chiral relatively stable allylic 1,4‐biradical. At infinite allene concentration the quantum yield approaches 1, indicating no energy loss during the reaction. Thus no measurable disproportionation of the allylic biradicals (Z)‐8 and (E)‐8 occurs.

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“…Jfingst wurden auch andere Thiet-Vertreter beschrieben (Brouwer, George, Seykens & Bos, 1978) und fiber R6ntgenstrukturanalysen von zwei Spiro[2H-thiet-2,9'-xanthen]-Derivaten berichtet (Verhoeckx, Kroon, Brouwer & Bos, 1980;de Vos, Kroon, Brouwer & Bos, 1981).…”

Section: Introductionunclassified

Die Strukturen von 1,3-Dimethyl-3',4'-diphenylimidazolidin-2-spiro-2'(2'H)-thiet-4,5-dion, 1,3-Dimethyl-4',5'-diphenylimidazolidin-2-spiro-3'(3'H)-1',2'-dithiol-4,5-dion und 1,3-Dimethyl-2-(1,2-diphenylethyl)imidazolidin-4,5-dion

Gotthardt¹,

Huss²

1982

Acta Crystallogr Sect B

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The first two title compounds are obtained from the light-induced reaction of 1,3-dimethyl-2-thioparabanic acid in the presence of diphenylacetylene, whereas the third product resulted from treatment of the first with Raney nickel. The structure of 1,3-dimethyl-3',4'-diphenylimidazolidine-2-spiro-2' (2'H)-thiete-4,5-dione (C19Ht6N202 S) was solved by direct methods and refined by least-squares techniques to a residual R index of 0.047 based on 2131 observations with I _> 2o(/). The compound crystallizes in the orthorhombic space group Pbca, with a = 14.

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Isolation of a crystalline thiete and its ‘open’ isomer; Photoproducts of xanthenethione and bis(tert-butylthio)ethyne

Cited by 22 publications

References 1 publication

Thiophosphonium–Alkyne Cycloaddition Reactions: A Heavy Congener of the Carbonyl–Alkyne Metathesis

Thiophosphonium–Alkyne Cycloaddition Reactions: A Heavy Congener of the Carbonyl–Alkyne Metathesis

Cycloaddition Reactions of Substituted Allenes with Triplet Excited Aromatic Thiones: Product Formation and Reaction Mechanism

Die Strukturen von 1,3-Dimethyl-3',4'-diphenylimidazolidin-2-spiro-2'(2'H)-thiet-4,5-dion, 1,3-Dimethyl-4',5'-diphenylimidazolidin-2-spiro-3'(3'H)-1',2'-dithiol-4,5-dion und 1,3-Dimethyl-2-(1,2-diphenylethyl)imidazolidin-4,5-dion

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