Synthesis and Cycloaddition Reactions of 1-(Arylthio)-1,3-dienes. A Combined Experimental and Theoretical Study of Bicyclic Adducts Structures

Maddaluno, Jacques; Gaonac'h, Odile; Marcual, Albert; Toupet, Loı̈c; Giessner‐Prettre, Claude

doi:10.1021/jo9519120

Cited by 27 publications

(21 citation statements)

References 59 publications

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“…Previously, Maddaluno and coworkers fully investigated the Diels-Alder reactions of the 1-(phenylthio)-4-substituted-1,3-butadienes with maleic anhydride or maleimides and reported the photochemical [1,3] sigmatropic shift of the phenylthio group of the adducts. 12) In our case, the normal [4ϩ2] adducts could not be observed in the reaction mixture of 2 and dienophiles. Furthermore, the product was the isoindole 5, not the 1,3-sulfenyl migrated products.…”

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confidence: 45%

A Novel Push-Pull Diels-Alder Diene: Reactions of 4-Alkoxy- or 4-Phenylsulfenyl-5-chalcogene-substituted 1-Phenylpenta-2,4-dien-1-one with Electron-Deficient Dienophiles.

Yoshimatsu

Hibino

Ishida

et al. 2002

CHEMICAL & PHARMACEUTICAL BULLETIN

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The Diels-Alder cycloadditions of heteroatom-functionalized 1,3-butadienes have provided a powerful means to synthesize a great variety of functionalized skeletons.1) Alkoxy-, trimethylsilyloxy, and sulfenyl 1,3-butadienes have been commonly used as an electron-rich diene.2,3) On the other hand, 2,4-pentadienoates and their analogs bearing alkoxy, alkylthio or arylthio groups have been developed in novel Diels-Alder reactions, which with dienophiles highly regioand stereoselectively give the [4ϩ2] cycloadducts as novel precursors for natural products or bioactive compounds. 4-7)In particular, much attention has been focused on the reactions of 5-alkoxypenta-2,4-dienoates with dienophiles bearing an electron-withdrawing group in view of the opposite regioselectivity that they show. 8,9) However, the reactions of the push-pull dienes need strict conditions such as high pressure and high temperature. 10) To find reactive push-pull dienes is highly important for synthetic organic chemistry. Recently, we have reported novel C-C bond formations of the 3-selenenyl-2-alkoxy-, 3-selenenyl-2-sulfenyl-, 3-sulfenyl-2-alkoxyallylic cations with phenyltrimethylsilyloxyethylene, which provided the 4-pentenophenones bearing 4-and 5-sulfenyl or selenenyl 4-alkoxy groups, in high yields.11) We have found that their reactions with acids or bases gave a variety of 1-phenyl-2,4-pentadien-1-ones bearing the 3-heteroatom, which are the highly reactive Diels-Alder dienes and their reactions with dienophiles were found to provide various cycloadducts. Although a small part of the results have already described in our previous report, we further investigated the Diels-Alder reactions of various dienes with dienophiles and their high reactivities were elucidated by the computational analysis. We also found the unique 1,3-hydride shift of 3a,6,7,7a-tetrahydro-1H-isoindole-1,3(2H)-diones obtained from the reactions with maleimides. Here we report the details of the Diels-Alder reactions of the 1-phenyl-2,4-pentadien-1-ones bearing 4-alkoxy or 4-sulfenyl group with dienophiles.The 1-phenyl-2,4-pentadien-1-ones 2, 3 and 4 were obtained by the treatment of 1-phenyl-4-penten-1-one 1 with NaOEt at 0°C as shown in Chart 1. The diene 2 and 4 was a mixture of 4Z-and 4E-isomers; however, the dienes 3 was exclusively obtained as a single isomer, (2E,4Z). The stereochemistries of 2 and 4 were determined by the nuclear Overhauser effects (NOE) experiments as shown in Fig. 1. Irradiation of 4E-5-H increased the intensity of the methylene protons of the ethoxy group (1%). On the other hand, the NOE enhancement of the corresponding protons of 4E-isomer was not observed. The same results were obtained from the NOE experiments of 4. 2-and 3-Olefinic protons were observed as the trans coupling constant by the 1 H-NMR spectrum (J 15 Hz). These spectral data shows the main isomer of 2 or 4 is (2E,4Z).Next, we examined the reaction of the diene 2 (4Z : 4Eϭ86 : 14) with N-phenylmaleimide to give 6-benzoyl-5-ethoxy-2-phenyl-3-(phenylselenenyl)-3a,6,7,7a-tetrahydr...

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confidence: 45%

A Novel Push-Pull Diels-Alder Diene: Reactions of 4-Alkoxy- or 4-Phenylsulfenyl-5-chalcogene-substituted 1-Phenylpenta-2,4-dien-1-one with Electron-Deficient Dienophiles.

Yoshimatsu

Hibino

Ishida

et al. 2002

CHEMICAL & PHARMACEUTICAL BULLETIN

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“…The chemical efficiency of this reaction is to be underlined in relation with a very comparable case in which the dienic moiety bears a thiophenyl substituent that totally inhibits the cycloaddition reaction. 9 Comments can be made on both the regiochemical and the stereochemical aspects.…”

Section: Resultsmentioning

confidence: 99%

“…Found: C,69.40;H,8. (3 H,s),m),2.75 (1 H,dt,4.4,9.5 Hz),3.03 (1 H,d,12.8 Hz),3.52 (1 H,d,12.8 Hz),3.65 (1 H,d,11.9 Hz),3.94 (1 H,bd,9.5 Hz),4.45 (1 H,d,11.9 Hz),5.30 (1 H, br s); trans-ring junction relationship, corresponding to the exo-approach; 13 C NMR (50 MHz, CDCl3) δ 20. 9,21.9,22.8,24.7,29.0,39.0,42.7,72.7,75.9,81.6,123.1,137.5,178.9. Anal.…”

Section: Methodsmentioning

confidence: 99%

Synthesis of Functionalized Trienes and Regioselective Formation of Medium-Ring Lactones through Intramolecular Diels−Alder Reaction

et al. 1996

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“…12) Recently, we reported the two-carbon homologations such as the asulfenyl 13,14) or a-selenenyl 15) formylation of aldehydes and ketones using b-alkoxyalkenyl lithiums. Next our attention has been focused on the four-carbon homologation of the carbonyl compounds.…”

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confidence: 99%

A Novel 3,4-Bis(sulfenyl)- or 4-Selenenyl-3-sulfenylpenta-2,4-dienylation of Aldehydes Using 4-Ethoxy-1,2-bis(sulfenyl)- or 1-Selenenyl-2-sulfenyl-buta-1,3-dienyl Lithiums

Yoshimatsu

Matsuura

Gotoh

2003

CHEMICAL & PHARMACEUTICAL BULLETIN

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Four-carbon homologation is one of the important processes in the syntheses of the polyene antibiotics and pheromones and other bioactive compounds.1-3) The most useful reagents are the triethyl phosphonoesters (HornerWadsworth-Emmons reagents) or the Wittig type reagents, which directly react with the aldehydes and ketones to give the penta-2,4-dienals.4-7) 4-Alkoxybuta-1,3-dienyl lithiums as the other useful reagents have been reported by Wollenberg or Duhamel to easily utilize the four-carbon homologation using 4-alkoxybuta-1,3-dienyl tributyltin, [8][9][10] chloride and bromides; 11) however, more functionalized 4-alkoxybuta-1,3-dienyl lithiums have been hitherto unknown.12) Recently, we reported the two-carbon homologations such as the asulfenyl 13,14) or a-selenenyl 15) formylation of aldehydes and ketones using b-alkoxyalkenyl lithiums. Next our attention has been focused on the four-carbon homologation of the carbonyl compounds. If a new 4-alkoxybuta-1,3-dienyl lithiums bearing an a-and b-sulfenyl or selenenyl functional groups would be generated, they will easily react with carbonyl compounds and the following hydrolysis to succeed a new type of four-carbon homologation of the carbonyl compounds. Now we here report a novel four-carbon homologation of aldehydes using 4-ethoxybuta-1,3-dienyl lithiums stabilized by the 1-and 2-chalcogene groups and its application to the synthesis of 2,4,6,8-nonatetraenal.First, we show the preparations of the dienes 5-8 in Chart 1. Phenyl propargyl sulfide 1a was treated with EtMgBr/ CH(OEt) 3 to give the acetal 2a, which easily isomerized to the allenyl sulfide 3 with NaOEt, the successive addition of thiophenol or 15% NaSMe in water to give (E)-and (Z)-but-3-enal acetals 4a and (E)-and (Z)-4b. Treatment of (E)-and (Z)-3,4-bis(sulfenyl)but-3-enal acetals with t-BuOK provided the titled 4-ethoxy-1,2-bis(sulfenyl)dienes 5 and 6 in good yields. The methanesulfenyl diene 5 is so labile at room temperature that it must be immediately used at the next step. Selenium derivatives 7 and 8 were also obtained by the same methods.Next, we examined the lithiation and the reaction of the 4-ethoxybuta-1,3-diene 5 with pivalaldehyde (Table 1). We found that 5 easily undergo lithiation with n-BuLi/DABCO at Ϫ50°C and react with pivalaldehyde afforded the pentadienyl alcohol 9a. The structure of 9a was determined by spectral and analytical data. The stereochemistry was elucidated by the 1 H-NMR coupling constants of the olefinic protons and the NOE experiments as 4E,6E. The reaction of the dienyl lithium with aldehydes was found to stereoselectively occur by the stabilizing effect of b-heteroatom substituents of the alkenyl lithiums. 16,17) The large excess of n-BuLi provided the deethoxylated penta-2,4-dienyl alcohol 10 (Entry 7). to high yields using 4-ethoxy-1-(benzenesulfenyl)-2-(methanesulfenyl)-(5), 4-ethoxy-1,2-bis(benzenesulfenyl)but-1,3-diene (6), and 1-selenenyl derivatives 7 and 8. This novel four-carbon homologation could be applied to a synthesis of 3,4,7,8-tetrakis(benzenes...

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Synthesis and Cycloaddition Reactions of 1-(Arylthio)-1,3-dienes. A Combined Experimental and Theoretical Study of Bicyclic Adducts Structures

Cited by 27 publications

References 59 publications

A Novel Push-Pull Diels-Alder Diene: Reactions of 4-Alkoxy- or 4-Phenylsulfenyl-5-chalcogene-substituted 1-Phenylpenta-2,4-dien-1-one with Electron-Deficient Dienophiles.

A Novel Push-Pull Diels-Alder Diene: Reactions of 4-Alkoxy- or 4-Phenylsulfenyl-5-chalcogene-substituted 1-Phenylpenta-2,4-dien-1-one with Electron-Deficient Dienophiles.

Synthesis of Functionalized Trienes and Regioselective Formation of Medium-Ring Lactones through Intramolecular Diels−Alder Reaction

A Novel 3,4-Bis(sulfenyl)- or 4-Selenenyl-3-sulfenylpenta-2,4-dienylation of Aldehydes Using 4-Ethoxy-1,2-bis(sulfenyl)- or 1-Selenenyl-2-sulfenyl-buta-1,3-dienyl Lithiums

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