A new approach to 2,2-disubstituted 1-(methylsulfanyl)vinyl phosphonates via an intermediate thiocarbonyl ylide

Mlostoń, Grzegorz; Urbaniak, Katarzyna; Linden, Anthony; Heimgartner, Heinz

doi:10.1016/j.tet.2009.07.074

Cited by 10 publications

(5 citation statements)

References 34 publications

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“…According to literature, reactions of diazafluorene with dipolarophiles, which have a heteroatomic core, occur mostly on O=C< [20,22] parts, creating oxadiazoline, -P=C< (phosphadiazoline) [23], and S=C< (thiadiazoline) [21,25].…”

Section: Reactions Of Diazafluorene With Dipolarophiles Which Has a Hmentioning

confidence: 99%

“…Similarly, reaction with 2-acetyl-5-methyl-1,2,3-diazaphosphole (48) leads to a cyclical product with a yield of 89%. The process is realised at a temperature of 20 o C and hexane as a solvent (time 3h) [21]. Diazafluorene (1) also reacts with dipolarophile with thiadiazoline group S=C<.…”

Section: Reactions Of Diazafluorene With Dipolarophiles Which Has a Hmentioning

confidence: 99%

“…A reaction with methyl diethoxyphosphinecarbodithioate 1-oxide ester (50) creates 1,3,4-thiadiazoline. The process is realised at a temperature of -65 o C and tetrahydrofuran as a solvent [21].…”

Section: Reactions Of Diazafluorene With Dipolarophiles Which Has a Hmentioning

confidence: 99%

“…The process of 1,3-dipolar cycloaddition (in brief 1,3DC) is the most universal method of creating five membered carbo-and heterocyclic compounds [13]. When using diazafluorene (as 1,3-dipole) as an addent, one can produce connections of a pyrazoline [11][12][13][14][15][16][17][18][19][20][21][22][23][24][25][26] skeleton within its structure. Those connections are valuable from a practical perspective [1][2][3][4][5][6][7][8][9][10].…”

Section: Introductionmentioning

confidence: 99%

“…Not all reactions between diazafluorene (1) and dipolarophile with an ethylene part result in a cyclic product. An example of an unexpected mechanism is a series of reactions with (E)-2-aryl-1-cyano-1-nitroethenes (21). They are realised at a temperature of 25 o C and benzene as a solvent, and lead to derivatives of hydrazines.…”

Section: Introductionmentioning

confidence: 99%

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Diazafluorene in 1,3-dipolar cycloaddiction reactions: short review

2018

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Section: Reactions Of Diazafluorene With Dipolarophiles Which Has a Hmentioning

confidence: 99%

Section: Reactions Of Diazafluorene With Dipolarophiles Which Has a Hmentioning

confidence: 99%

Section: Reactions Of Diazafluorene With Dipolarophiles Which Has a Hmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Diazafluorene in 1,3-dipolar cycloaddiction reactions: short review

2018

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Twofold Extrusion Reactions

Guziec

2012

Organic Reactions

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Twofold extrusion reactions are chemical transformations in which two small inorganic molecules or atoms connecting carbon or nitrogen atoms are lost, generating the corresponding carbon‐carbon or carbon‐nitrogen double bonds. These reactions are particularly useful for the preparation of sterically hindered alkenes and imines. The inorganic species liberated in twofold extrusion reactions can be molecular nitrogen, sulfur, selenium, tellurium, sulfur dioxide, sulfur monoxide, carbon dioxide or carbon monoxide. The most common precursors for twofold extrusion reactions are 1,3,4‐thiadiazolines, which thermally extrude molecular nitrogen affording thiiranes. These thiiranes can be readily desulfurized to afford the corresponding alkenes using tertiary phosphines. The corresponding 1,3,4‐selenadiazolines thermally extrude both molecular nitrogen and atomic selenium directly affording alkenes. Alkenes can also be prepared by formal extrusions of molecular nitrogen plus sulfur dioxide or sulfur monoxide. Extremely sterically hindered imines can be prepared by extrusions of molecular nitrogen and sulfur or selenium from in situ generated heterocyclic precursors. Other less common twofold extrusion reactions are also reported. The detailed preparations of the required precursors for the twofold extrusion reactions as well as the mechanisms of these extrusion processes are discussed in this chapter. The utility of twofold extrusion reactions in the preparations of ‘molecular rotors’ and other extremely sterically hindered alkenes is presented. The steric limitations of the twofold extrusion reactions are discussed along with comparisons of these reactions with other alkene‐ and imine‐forming synthetic methods. The Tabular Survey covers material through the end of 2009.

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Reactions of Cycloaliphatic Thioketones and Their Oxo Analogues with Lithiated Methoxyallene: A New Approach to Vinylthiiranes

Jasiński

Mlostoń

Stolarski

et al. 2014

Chemistry An Asian Journal

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Admantanethione smoothly reacted with lithiated methoxyallene at low temperatures yielding the expected allenyl-substituted thiolate, which upon aqueous work-up underwent spontaneous 1,3-cyclization to afford a hitherto unknown methoxy-substituted vinylthiirane derivative. The analogous reaction with adamantanone led to the corresponding allenyl alcohol that can be isolated and--depending on the conditions applied--either be converted into the corresponding vinyloxirane or into the 2,5-dihydrofuran derivative. Sterically more crowded thioketones were also combined with lithiated methoxyallene, but in these cases competitive 1,5-cyclization leading to isomeric dihydrothiophene derivatives was observed. DFT calculations of model intermediates and products show distinct energy differences of the sulfur and the corresponding oxygen compounds. Desulfurization of the adamantanethione-derived vinylthiirane yielded a methoxy-substituted 1,3-diene that was studied in cycloadditions with electron-deficient dienophiles. Whereas in the case of tetracyanoethylene the corresponding cyclobutane derivative was formed, the reaction with nitrosobenzene provided the expected 1,2-oxazine derivative. By reductive cleavage of the N-O bond this heterocycle was converted into an unsaturated amino alcohol bearing an adamantane moiety.

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A new approach to 2,2-disubstituted 1-(methylsulfanyl)vinyl phosphonates via an intermediate thiocarbonyl ylide

Cited by 10 publications

References 34 publications

Diazafluorene in 1,3-dipolar cycloaddiction reactions: short review

Diazafluorene in 1,3-dipolar cycloaddiction reactions: short review

Twofold Extrusion Reactions

Reactions of Cycloaliphatic Thioketones and Their Oxo Analogues with Lithiated Methoxyallene: A New Approach to Vinylthiiranes

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