n-Butyl-lithium-induced cleavage of several dithioacetals derived from diaryl ketones

Ikehira, Hideyuki; Tanimoto, Shigeo; Oida, Tatsuo

doi:10.1039/p19840001223

Cited by 20 publications

(8 citation statements)

References 2 publications

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“…8 This facile fission of the ring and the formation of the products have been attributed to the attack on sulfur by the alkyl anion, followed by hydrogen abstraction. Anion-induced gas phase deprotonation has been described to result in the cleavage of the dithiane ring and to form 1-allylthiomethylthiyl anion intermediate.…”

Section: Resultsmentioning

confidence: 99%

“…16 The GC-MS analysis of the product of the reaction of 1,3-dithiane (1) with trifluoromethylthiocopper (2) indicated the presence of the following compounds (cf. Figure 1): (1) 1,3-dithiane (1); (2) 1,3-dithiolane (3); (3) bis-(tri-fluoromethyl)disulfide (4); (4) 1-(trifluoromethylthio)-3-(trifluoromethylthio-methyl)-1,3-propanedithiol (5); (5) 2-methyl-1,3-dithiane: (6); bis-(1,3-dimethyl)-1,3-propanedithiol (7); and (6) l-methyl-1,3-propanedithiol (8). The presence of 1,3-dithialane (3) was somewhat surprising in that its origin could not be immediately traced.…”

Section: Resultsmentioning

confidence: 99%

“…18 The suggested attack on the sulfur atom of 1,3-dithiane (1) has precedent ( Figure 3). 8 It is worth noting that the presence of the sulfur anion analog of intermediate 14 has been invoked to rationalize the gas-phase cleavage reaction of 1,3-dithiane (1). 9b Table I describes the mass spectral fragmentation of the compounds mentioned in the text.…”

Section: Figurementioning

confidence: 99%

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Reaction of 1,3-Dithiane with Trifluoromethylthiocopper

Munavalli

Rohrbaugh

Rossman

et al. 2006

Phosphorus, Sulfur, and Silicon and the Related Elements

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The 1,3-dithiane ring undergoes cleavage even under mild neutral reaction conditions when heated in the presence of trifluoromethylthiocopper. The freeradical nature of the reaction was confirmed by the characterization of bis-(trifluoromethyl)disulfide as one of the products.Since the 1970s 1, 3-dithiane (1) has been employed extensively as a building block in the preparation of a vast array of organic intermediates and synthons required for the total synthesis of several scores of interesting organic compounds. The synthetic utility and usefulness of 1,3-dithiane (1) rest squarely on the facile introduction of functional groups and the removal of the masking moiety, namely the 1,3-propanedithiol fragment after the accomplishment of the successful synthesis. The pioneering work of Corey and Seebach 1 has demonstrated the synthetic utility and versatility of the dithiane synthons. The chemistry of dithiane and dithialanes has been reviewed. 2 An excellent report on the synthetic applications of the anions derived from 1,3-dithiane has been published. 2c In this context, it is worth mentioning that the dithiane ring system has been modified to 1,3-oxathiane and its synthetic applications have been described. 3

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Figurementioning

confidence: 99%

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Reaction of 1,3-Dithiane with Trifluoromethylthiocopper

Munavalli

Rohrbaugh

Rossman

et al. 2006

Phosphorus, Sulfur, and Silicon and the Related Elements

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“…Since the ketone lacks the hydrogen at the carbonyl carbon, dihydrofuran derivative with an exocyclic double bond 65 is obtained in satisfactory yield [Equation (26)]. Since the ketone lacks the hydrogen at the carbonyl carbon, dihydrofuran derivative with an exocyclic double bond 65 is obtained in satisfactory yield [Equation (26)].…”

Section: Miscellaneous Reactionsmentioning

confidence: 99%

“…Several sites in the dithioacetal group are known to react with alkyllithiums. [26] Organocopper reagents behave similarly [Equation (9)]. Deprotonation at C 2 or C 4 has been shown to result in fragmentation of five-membered heterocycles.…”

Section: Introductionmentioning

confidence: 99%

Dithioacetals as Zwitterion Synthons

Luh

Lee

2005

Eur J Org Chem

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This microreview highlights recent advances in the synthetic applications of dithioacetal functionality. Propargylic dithioacetals and related compounds have been shown to be useful, with the aid of thiophilic organolithium or organocopper reagents, for the synthesis of polysubstituted allenes, trisubstituted furans, and pyrroles. An extension of this annulation reaction to the bidirectional iterative synthesis of furan‐containing oligoaryls and to cyclophane synthesis is described. Alternatively, the convergent synthesis of such oligoaryls from propargylic dithioacetals is briefly discussed. Not only can the carbon–sulfur bonds in dithioacetals be readily displaced by carbon–carbon and/or carbon–heteroatom bonds, but in addition a range of reactions involving polarity inversion in neighboring carbon atoms can also take place. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)

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