First Photolysis of an Enolizable 1,4-Dithioketone: Photochemical Study of Bis-thiocamphor

Salama, Paul; Poirier, Marc; Maya, Maria del Rocio Patiño; Robichaud, Jacques; Benoit, M.

doi:10.1055/s-1996-5614

Cited by 7 publications

(14 citation statements)

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“…General Procedure for Aerobic Oxidation of 4H-Selenopyran-4-Selones (7,8). A CHCl 3 solution of symmetrical or unsymmetrical 4H-selenopyran-4-selone (7 or 8, 1.00 mmol) was standing at room temperature for 1 week, and the reaction mixture was filtered to remove the elemental selenium.…”

Section: Physical and Spectral Data For Unsymmetrical 4h-selenopyran-mentioning

confidence: 99%

“…Our previous attempts for the synthesis of dibornenyl diselenide using our procedure starting from dcamphor ptoluenesulfonylhydrazone (1) also resulted in the complex mixture containing dibornylene (3), 1,4-diselenin (4), 1,2,5-triselenepin (5), and a few uncharacterized compounds along with the formation of dibornenyl diselenide (2). 18 Therefore, we just started the investigation of the structural confirmation of these uncharacterized byproducts in order to obtain a key for the optimization of the reaction conditions, and after several efforts, we could isolate and characterize the structures of some of these byproducts involving a hitherto unknown purple-colored stable crystalline compounds, 1,6,6αλ 4 -triselenapentalene (6), and an isomeric mixture of greenish brown-colored 4H-selenopyran-4-selones (7,8) fused with two bornane skeletons.…”

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confidence: 99%

“…73 In conclusion, we found a new method for the synthesis of 1,6,6αλ 4 -triselenapentalene (6) and 4H-selenopyran-4-selones Scheme 5. Oxidation of 1,6,6aλ 4 -triselenapentalene 6and 4H-selenopyran-4-selones (7,8). c A DMF solution of 1 was treated with t-BuOK and elemental selenium under an argon atmosphere and then dry CO 2 gas was introduced to the reaction atmosphere along with an additional heating for 1.5 hours.…”

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confidence: 99%

“…An ORTEP drawing of 4H-selenopyran-4-selone(8). Conversion of symmetrical 1,2,5-triselenepin (5) into 1,4-diselenin(4).…”

mentioning

confidence: 99%

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Formation of a Sterically Crowded 1,6,6αλ⁴-Triselenapentalene and 4H-Selenopyran-4-selones Fused with Two Bornane Skeletons Through the Reaction of d-Camphor p-Toluenesulfonylhydrazone With a Base and Elemental Selenium

Shimada

Aoyagi

Takikawa

2020

Natural Product Communications

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Reaction of d-camphor p-toluenesulfonylhydrazone with t-butoxide and elemental selenium in dimethylformamide at an elevated temperature afforded a stable compound having a unique 1,6,6αλ4-triselenapentalene ring and 4 H-selenopyran-4-selones along with dialkenyl diselenide, dibornylenes, and 1,2,5-triselenepin, and the structural confirmation of these products were carried out by X-ray crystallographic analysis. The sterically crowded 1,6,6aλ4-triselenapentalene ring fused with two bornane sleketons was stable enough under aerobic exposure and was inactive toward sodium borohydride reduction but was converted into 1,2-diselenole derivative through m-chloroperbenzoic acid oxidation.

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Section: Physical and Spectral Data For Unsymmetrical 4h-selenopyran-mentioning

confidence: 99%

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confidence: 99%

mentioning

confidence: 99%

“…An ORTEP drawing of 4H-selenopyran-4-selone(8). Conversion of symmetrical 1,2,5-triselenepin (5) into 1,4-diselenin(4).…”

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Formation of a Sterically Crowded 1,6,6αλ⁴-Triselenapentalene and 4H-Selenopyran-4-selones Fused with Two Bornane Skeletons Through the Reaction of d-Camphor p-Toluenesulfonylhydrazone With a Base and Elemental Selenium

Shimada

Aoyagi

Takikawa

2020

Natural Product Communications

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“…were readily prepared by aldol condensation of natural (+)-camphor (4) with salicyl aldehyde (5), followed by introduction of a dienophile moiety with 7 to 6 (Scheme 1). When the ketones (1) were thionated with Lawesson's reagent (LR) in refluxing toluene or xylene for 1.5-3 h, the formed thioketones (2) smoothly underwent the intramolecular [4+2] cycloaddition to afford the cycloadducts (3) in good yields (Table 1).…”

Section: -(Arylmethylene)camphorsmentioning

confidence: 99%

Synthesis of Bornene Ring-fused Dihydrothiopyrans, a New Class of Chiral Cyclic Sulfides, via Intramolecular Hetero Diels-Alder Reaction of Homochiral Thiabutadienes, 3-(Arylmethylene)thiocamphors

Saito¹,

Furuie²,

Ishigo-oka³

et al. 2000

HETEROCYCLES

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A highly diastereoisoface-selective intramolecular hetero Diels-Alder reaction of homochiral camphor-derived thiabutadienes to afford novel, optically active bornene ring-fused dihydrothiopyrans is described for the first time.Thiocarbonyl compounds have recently received considerable attention as synthetic tools with specific properties. 1 In fact, such useful sulfur compounds have been proved as key intermediates with rich, specific reactivity in the synthesis of complex molecules and natural products. 2 On the other hand, there are numerous examples of camphor derivatives that have been exploited, particularly as chiral sources. 3 The attractive advantages of employing camphor in asymmetric synthesis are its relatively inexpensive and easy availability, potent transformation ability, and promising asymmetric induction due to the topological differentiation efficiency apparently by virtue of the rigid framework of its derivatives. Salama et al. recently reported the photolysis of thiocamphor for the synthesis of the 3,6-dihydro-1,2dithiin system. 4 Corre et al. have recently demonstrated that thiocamphor derivatives can also be utilized as useful synthons for chiral ligands. 5 Some recent reports also describe the synthesis of homochiral camphor-annulated (fused) heterocycles such as pyridines, 6 pyrroles, 7 pyrazoles, 8 and oxazolines, 9 particularly for the use of chiral ligands. To the best of our knowledge, however, there have been no reports so far of the synthesis of bornene-fused homochiral dihydrothiopyrans. In the course of our investigation on α,β-unsaturated thiocarbonyl compounds, we have reported asymmetric hetero Diels-Alder (HDA) reactions of thiabutadienes to afford optically active dihydrothiopyrans. 10 We considered it worthwhile to incorporate the camphor framework into a heterodiene system for preparing a new chiral thiabutadiene. Furthermore, to the best of our knowledge, there have been no reports on the intramolecular, asymmetric thiabutadiene-Diels-Alder reaction. 11,12 Here, we wish to report for the first time the synthesis of optically active, bornene-fused dihydrothiopyrans that involves a highly diastereoisoface-selective intramolecular HDA cycloaddition of 3-(arylmethylene)thiocamphors bearing a dienophile (2).

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ChemInform Abstract: First Photolysis of an Enolizable 1,4‐Dithioketone: Photochemical Study of Bis‐thiocamphor.

et al. 1997

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First Photolysis of an Enolizable 1,4-Dithioketone: Photochemical Study of Bis-thiocamphor. -The photolysis of the bis-thiocamphor (I) results in formation of the mercapto-enethione (II) via 1,5 abstraction and 1,5 H-shift. This stands in contrast to the analogous reaction of thiocamphor, where only the β-endo hydrogen migrates to the sulfur. -(SALAMA, P.; POIRIER, M.; DEL ROCIO PATINO MAYA, M.; ROBICHAUD, J.; BENOIT, M.; Synlett (1996) 9, 823-824; Dep. Chim. Biochim., Univ. Moncton, Moncton, New Brunswick E1A 3E9, Can.; EN)

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First Photolysis of an Enolizable 1,4-Dithioketone: Photochemical Study of Bis-thiocamphor

Cited by 7 publications

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Formation of a Sterically Crowded 1,6,6αλ⁴-Triselenapentalene and 4H-Selenopyran-4-selones Fused with Two Bornane Skeletons Through the Reaction of d-Camphor p-Toluenesulfonylhydrazone With a Base and Elemental Selenium

Formation of a Sterically Crowded 1,6,6αλ⁴-Triselenapentalene and 4H-Selenopyran-4-selones Fused with Two Bornane Skeletons Through the Reaction of d-Camphor p-Toluenesulfonylhydrazone With a Base and Elemental Selenium

Synthesis of Bornene Ring-fused Dihydrothiopyrans, a New Class of Chiral Cyclic Sulfides, via Intramolecular Hetero Diels-Alder Reaction of Homochiral Thiabutadienes, 3-(Arylmethylene)thiocamphors

ChemInform Abstract: First Photolysis of an Enolizable 1,4‐Dithioketone: Photochemical Study of Bis‐thiocamphor.

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First Photolysis of an Enolizable 1,4-Dithioketone: Photochemical Study of Bis-thiocamphor

Cited by 7 publications

References 0 publications

Formation of a Sterically Crowded 1,6,6αλ4-Triselenapentalene and 4H-Selenopyran-4-selones Fused with Two Bornane Skeletons Through the Reaction of d-Camphor p-Toluenesulfonylhydrazone With a Base and Elemental Selenium

Formation of a Sterically Crowded 1,6,6αλ4-Triselenapentalene and 4H-Selenopyran-4-selones Fused with Two Bornane Skeletons Through the Reaction of d-Camphor p-Toluenesulfonylhydrazone With a Base and Elemental Selenium

Synthesis of Bornene Ring-fused Dihydrothiopyrans, a New Class of Chiral Cyclic Sulfides, via Intramolecular Hetero Diels-Alder Reaction of Homochiral Thiabutadienes, 3-(Arylmethylene)thiocamphors

ChemInform Abstract: First Photolysis of an Enolizable 1,4‐Dithioketone: Photochemical Study of Bis‐thiocamphor.

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Formation of a Sterically Crowded 1,6,6αλ⁴-Triselenapentalene and 4H-Selenopyran-4-selones Fused with Two Bornane Skeletons Through the Reaction of d-Camphor p-Toluenesulfonylhydrazone With a Base and Elemental Selenium

Formation of a Sterically Crowded 1,6,6αλ⁴-Triselenapentalene and 4H-Selenopyran-4-selones Fused with Two Bornane Skeletons Through the Reaction of d-Camphor p-Toluenesulfonylhydrazone With a Base and Elemental Selenium