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Synlett
Volumn , Issue 9, 2008, Pages 1376-1380
Iridium- and rhodium-catalyzed [2+2+2] cycloadditions of diynes with maleimide: A new synthetic route to highly substituted phthalimides
Author keywords

Alkyne cycloaddition; Dehydrogenations; Iridium; Phthalimides; Rhodium
Indexed keywords

ALKYNE DERIVATIVE; IRIDIUM; MALEIMIDE; PHTHALIMIDE DERIVATIVE; RHODIUM;
EID: 45749089419     PISSN: 09365214     EISSN: None     Source Type: Journal    
DOI: 10.1055/s-2008-1072746     Document Type: Article
Times cited : (12)
References (46)
  • 1
    • 35148843206 scopus 로고    scopus 로고
    • For reviews, see: a
    • For reviews, see: (a) Recupero, F.; Punta, C. Chem. Rev. 2007, 107, 3800.
    • (2007) Chem. Rev , vol.107 , pp. 3800
    • Recupero, F.1    Punta, C.2
  • 31
    • 0034602280 scopus 로고    scopus 로고
    • For an example of cycloaddition of three alkynes in the presence of a maleimide double bond, see
    • (g) For an example of cycloaddition of three alkynes in the presence of a maleimide double bond, see: Grigg, R.; Sridharan, V.; Wang, J.; Xu, J. Tetrahedron 2000, 56, 8967.
    • (2000) Tetrahedron , vol.56 , pp. 8967
    • Grigg, R.1    Sridharan, V.2    Wang, J.3    Xu, J.4
  • 34
    • 45749115288 scopus 로고    scopus 로고
    • 2 (0.025 mmol) and DPPE (0.050 mmol) were dissolved in degassed THF (5 mL) under an Ar atmosphere and the mixture was stirred at r.t. for 5 min. Maleimide (0.25 mmol) was then added in one portion and the reaction mixture was refluxed for 3 h in the case of iridum catalysis or 24 h in the case of rhodium catalysis. After cooling, the resulting reaction mixture was concentrated under reduced pressure and cyclohexadiene 3 was isolated by column chromatography.
    • 2 (0.025 mmol) and DPPE (0.050 mmol) were dissolved in degassed THF (5 mL) under an Ar atmosphere and the mixture was stirred at r.t. for 5 min. Maleimide (0.25 mmol) was then added in one portion and the reaction mixture was refluxed for 3 h in the case of iridum catalysis or 24 h in the case of rhodium catalysis. After cooling, the resulting reaction mixture was concentrated under reduced pressure and cyclohexadiene 3 was isolated by column chromatography.
  • 35
    • 45749126931 scopus 로고    scopus 로고
    • General Procedure for the Preparation of Diynes 1 by Sonogashira Coupling An oven-dried flask was charged with the corresponding aryl iodide (15 mmol, PdCl2(PPh3)2 (350 mg, 0.50 mmol, anhyd CuI (38 mg, 0.2 mmol, dried Et3N (15 mL) and anhyd THF (15 mL) under Ar. The mixture was then stirred at r.t. for 10 min. Afterwards, a solution of the corresponding diacetylene (5 mmol) in anhyd THF (15 mL) and dried Et3N (15 mL) was added dropwise. The reaction mixture was stirred at r.t. for 48 h under Ar. The reaction mixture was poured into an aq soin of 10% HCl and was extracted with Et2O. The organic phases were washed with H2O, brine, and dried over Na2SO4. Evaporation of the solvent gave a brown oil or solid from which the product was separated by column chromatography over silica gel using a mixture of EtOAc-pentane (1:1) to give the product 1 with analytical purity in 80-95
    • 4. Evaporation of the solvent gave a brown oil or solid from which the product was separated by column chromatography over silica gel using a mixture of EtOAc-pentane (1:1) to give the product 1 with analytical purity in 80-95% yield. All diynes 1 gave analytical and spectral data in accordance with the structure.
  • 36
    • 45749139542 scopus 로고    scopus 로고
    • All cyclohexadienes 3 gave analytical and spectral data in accordance with the structure. Data for Products 3 Compound 3a: mp 171.5°C 1H NMR (400 MHz, CDCl3, δ, 8.08 (br s, 1 H, 7.28-7.43 (m, 10 H, 4.28 (s, 2 H, 4.17 (q, 2 H, J, 8.0 Hz, 4.03 (q, 2 H, J, 8.0 Hz, 3.15 and 3.08 (ABq, 4 H, J, 20.0 Hz, 1.21 (t, 3 H, J, 8.0 Hz, 1.08 (t, 3 H, J, 8.0 Hz, 13C NMR (100 MHz, CDCl3, δ, 176.4, 170.9, 170.8, 138.5, 135.1, 128.4, 128.1, 127.7, 124.0, 61.9, 61.7, 58.3, 47.9, 39.5, 14.1, 14.0. IR (neat, 3153, 3052, 1779, 1751, 1697, 1574, 1493, 1235, 1183 cm -1. Anal. Calcd for C29H27NO6: C, 71.74; H, 5.61; N, 2.88. Found: C, 71.48; H, 5.66; N, 2.53. Compound 3b: mp 253.5°C (dec, 1H NMR (400 MHz, DMSO-d6, δ, 11.36 (br s, 1 H, 7.29-7.42 (m, 10 H, 4.74 and 4.30 ABq, 4 H, J
    • 8: C, 68.25; H, 5.73; N, 2.57. Found: C, 68.14; H, 5.66; N, 2.41.
  • 40
    • 33947094357 scopus 로고
    • For classical aromatization reagents, see
    • For classical aromatization reagents, see: Fu, P. P.; Harvey, R. G. Chem. Rev. 1978, 78, 317.
    • (1978) Chem. Rev , vol.78 , pp. 317
    • Fu, P.P.1    Harvey, R.G.2
  • 45
    • 45749114463 scopus 로고    scopus 로고
    • General Procedure for Aromatization of Cyclohexadienes 3 With DDQ: Cyclohexadiene 3 (0.15 mmol) and DDQ (0.15 mmol) were dissolved in anhyd toluene (5 mL) and the reaction mixture was stirred under reflux for 24 h. Once cooled, the resulting reaction mixture was washed with distilled H 2O, dried with Na2SO4, and evaporated under reduced pressure. Phthalimide 4 was obtained after chromatographical purification using SiO2. With MnO2: Cyclohexadiene 3 (0.15 mmol) and activated MnO2 (1.5 mmol) were added to anhyd toluene (5 mL, The black suspension was stirred under reflux for 48 h or until completion of the reaction TLC monitoring, After cooling, the solid was filtered off and the filtrate evaporated under reduced pressure, giving pure 4 in quantitative yields
    • 2 (1.5 mmol) were added to anhyd toluene (5 mL). The black suspension was stirred under reflux for 48 h or until completion of the reaction (TLC monitoring). After cooling, the solid was filtered off and the filtrate evaporated under reduced pressure, giving pure 4 in quantitative yields.
  • 46
    • 45749149448 scopus 로고    scopus 로고
    • 6: C, 72.04; H, 5.21; N, 2.90. Found: C, 72.35; H, 5.59; N, 3.12.
    • 6: C, 72.04; H, 5.21; N, 2.90. Found: C, 72.35; H, 5.59; N, 3.12.

* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.