SupplementaryData
Cobalt(Ӏ)-Catalyzed [6π+2π] Cycloadditions of 1,2-dienes to 1,3,5,7-cyclooctatetraene
Vladimir A. D’yakonov*, Gulnara N. Kadikova, Guzel F. Gazizullina,
Leonard M. Khalilov, andUsein M. Dzhemilev
Institute of Petrochemistry and Catalysis of RAS,
Prospect Oktyabrya 141, 450075, Ufa, Russian Federation
Fax: +7 347 2842750
E-mail: ,
Experimental Section
All solvents were dried (dichloroethane over P2O5) and freshly distilled before use. All reactions were carried out under a dry argon atmosphere. The reaction products were analyzed using chromatography on a Shimadzu GC-9A instrument(2000 x 2 mm column packed with 5% of SE-30 and 15% PEG-6000 on Chromaton N-AW, carrier gas – He). Mass spectral measurements were performed on a Shimadzu GCMS-QP2010 Plus at 70 eV and working temperature 200 oC. Elemental analysis of samples was determined on element analysator of Carlo Erba, model 1106. The 1H and 13С NMR spectra were recorded as CDCl3 solutions on spectrometer Bruker Avance-500 (125 MHz for 13C and 500 MHz for 1H). The chemical shifts are reported as δ values in ppm relative to internal standard Me4Si. 13C NMR spectra were edited by J-modulation (JMOD) on CH constants. Used a commercially available CoI2, 1,2-bis(diphenylphosphino)ethane, ZnI2, Zn, 1,3,5,7-cyclooctatetraene (Aсros Organics). 1,2-dienes were prepared according to literature procedures. 1,2
Cyclocodimerization of 1,3,5,7-cyclooctatetraene and 1,2-dienes (general procedure). Zinc powder (30 mol %) was added to a solution of CoI2 (10 mol %), dppe (10 mol%) in C2H4Cl2 (1.5 mL) in a glass ampoule in a dry argon atmosphere, and the mixture was stirred at room temperature for two minutes. Then COTT (1.0 mmol), 1,2-diene (1.5 mmol) in C2H4Cl2 (1.5 mL), and dry zinc iodide (20 mol %) were successively added. Then the ampoule was sealed. After heating at 60 oC for 20 hours the ampoule was opened, the reaction was stopped by the addition of petroleum ether and by stirring in air for 10 minutes to deactivate the catalyst. After filtration on a short pad of silica volatile solvents were removed under vacuum. Chromatographic purification on an SiO2 (100% petroleum ether as eluent) afforded the target products 2a-e, 4.
9-[(E)pentylidene]bicyclo[4.2.2]deca-2,4,7-triene (2a): Yield 80%, as colorless oil. nd20 1.5749. Rf 0.64. 1Н NMR (500 MHz, CDCl3): δ 6.09 (dd, J = 7 Hz, J = 12 Hz, 1Н), 6.07 (dd, J = 9 Hz, J = 12 Hz, 1Н), 5.94 (dd, J = 7 Hz, J = 9 Hz, 1Н), 5.80 (dd, J = 7 Hz, J = 9 Hz, 1Н), 5.73 (dd, J = 8 Hz, J = 12 Hz, 1Н), 5.63 (dd, J = 8 Hz, J = 12 Hz, 1Н), 5.13 (t, J = 7 Hz, 1Н), 3.38 (dd, J = 9 Hz, J = 7 Hz, 1Н), 2.84-2.86 (m, 1Н), 2.83 (d, J = 17 Hz, 1Н), 2.34 (dd, J = 17 Hz, J = 6 Hz, 1Н), 1.94-2.02 (m, 2Н), 1.33–1.36 (m, 4Н), 0.92 (t, J = 7 Hz, 3Н) ppm. 13С NMR (125 MHz, CDCl3): δ 139.82, 139.17, 138.84, 124.99, 124.89, 124.71, 123.72, 123.61, 42.25, 33.48, 32.71, 31.63, 27.56, 22.43, 14.06 ppm. MS m/z (EI, 70 eV) m/z (%): 200 [M]+(17), 157 (19), 143 (69), 129 (21), 115 (43), 91 (9), 77 (20), 67 (13), 41 (18). Anal. Calcd for С15H20: С, 89.94; Н, 10.06. Found: Found: С, 89.73; Н, 9.97.
9-[(E)-phenylmethylidene]bicyclo[4.2.2]deca-2,4,7-triene (2b): Yield 85%, as pale yellow oil.nd20 1.6332. Rf0.59.1Н NMR (500 MHz, CDCl3): δ 7.36 (t, J = 8 Hz, 2Н), 7.29 (d, J = 8 Hz, 2Н), 7.23 (t, J = 8 Hz, 1Н), 6.27 (s, 1Н), 6.18–6.22 (m, 1Н), 6.08–6.12 (m, 1Н), 6.02 (dd, J = 7 Hz, J = 9 Hz, 1Н), 5.87 (dd, J = 7 Hz, J = 9 Hz, 1Н), 5.77–5.79 (m, 1Н), 5.72–5.76 (m, 1Н), 3.59 (dd, J = 7 Hz, J = 9 Hz, 1Н), 3.19 (d, J = 17 Hz, 1Н), 2.86–2.91 (m, 1Н), 2.69 (ddd, J = 17 Hz, J = 7 Hz, J = 3 Hz, 1Н) ppm. 13С NMR (125 MHz, CDCl3): δ 143.87, 138.88, 138.42, 138.17, 128.85 (2C), 128.05 (2C), 125.98, 124.86, 124.78, 124.62, 124.35, 123.78, 43.08, 35.19, 32.85 ppm. MS m/z (EI, 70 eV) m/z (%): 220 [M]+ (15), 203 (9), 189 (6), 178 (7), 165 (10), 141 (20), 129 (100), 115 (64), 104 (22), 91 (82), 77 (40), 65 (34), 51(36), 39 (54). Anal. Calcd for С17H16: С, 92.68; Н, 7.32. Found: С, 92.52; Н, 7.38.
9-[(E)-2-phenylethylidene)bicyclo[4.2.2]deca-2,4,7-triene (2c):Yield 82%, as pale yellow oil.nd20 1.6449. Rf0.62.1Н NMR (500 MHz, CDCl3): δ 7.40 (t, J = 8 Hz, 2Н), 7.29–7.32 (m, 3Н), 6.21–6.23 (m, 2Н), 6.18–6.20 (m, 1Н), 6.07 (dd, J = 7 Hz, J = 9 Hz, 1Н), 5.93 (dd, J = 7 Hz, J = 9 Hz, 1Н), 5.87-5.90 (m, 1Н), 5.78 (dd, J = 12 Hz, J = 8 Hz, 1Н), 5.45 (t, J = 7 Hz, 2Н), 3.55 (dd, J = 9 Hz, J = 7 Hz, 1Н), 3.06 (d, J = 17 Hz, 1H), 2.97 (dd, J = 8 Hz, J = 15 Hz, 1Н), 2.54 (dd, J = 7 Hz, J = 17 Hz, 1Н) ppm. 13С NMR (125 MHz, CDCl3): δ 141.34, 141.28, 139.12, 138.86, 128.50 (2C), 128.49 (2C), 125.91, 125.04, 125.03, 123.91, 123.75, 123.35, 42.18, 34.16, 33.77, 32.77 ppm. MS m/z (EI, 70 eV) m/z (%): 234 [M]+ (45), 219 (71), 204 (32), 191 (19), 178 (18), 165 (13), 143 (82), 129 (75), 115 (54), 105 (61), 91 (100), 77 (35), 65(14), 51 (18), 41 (4). Anal. Calcd for С18H18: С, 92.26; Н, 7.74. Found: С, 92.03; Н, 7.69.
9-(diphenylmethylene)bicyclo[4.2.2]deca-2,4,7-triene (2d): Yield 78%, as light yellow solid, mp 119 oC. nd20 1.6470. Rf 0.49. 1Н NMR (500 MHz, CDCl3): δ 7.28-7.35 (m, 4Н), 7.20-7.27 (m, 6Н), 6.07 (dd, J = 9 Hz, J = 12 Hz, 1Н), 5.93 (dd, J = 7 Hz, J = 9 Hz, 1Н), 5.85 (dd, J = 8 Hz, J = 12 Hz, 1Н), 5.79 (m, dd, J = 9 Hz, J = 12 Hz, 1Н), 5.76 (dd, J = 7 Hz, J = 9 Hz, 1Н), 5.70 (dd, J = 8 Hz, J = 12 Hz, 1Н), 3.53 (dd, J = 7 Hz, J = 9 Hz, 1Н), 2.87 (dd, J = 12 Hz, J = 1 Hz, 1Н), 2.79-2.84 (m, 1Н), 2.55 (dd, J = 7 Hz, J = 12 Hz, 1Н) ppm. 13С NMR (125 MHz, CDCl3): δ 143.46, 142.68, 139.45, 138.79, 138.26, 136.79, 129.19 (4C), 128.16 (2C), 128.06 (2C), 126.36, 126.19, 125.50, 125.26, 123.58, 122.89, 38.50, 37.16, 33.28 ppm. MS m/z (EI, 70 eV) m/z (%): 296 [M]+ (72), 281 (36), 267 (18), 239 (18), 215 (27), 207 (100), 178 (8), 165 (47), 129 (46), 115 (26), 91 (47), 73 (51), 57 (13), 43 (14).Anal. Calcd for С23H20: С, 93.20; Н, 6.80. Found: С, 93.04; Н, 6.82.
9-[(E)-1-phenylethylidene)bicyclo[4.2.2]deca-2,4,7-triene (2e): Yield 83%, as pale yellow oil.nd20 1.5760. Rf0.60.1Н NMR (500 MHz, CDCl3): δ 7.34 (t, J = 8 Hz, 2Н), 7.23 (t, J = 8 Hz, 1Н), 7.13 (d, J = 8 Hz, 2Н), 6.27 (dd, J = 9 Hz, J = 11 Hz, 1Н), 6.13 (dd, J = 6 Hz, J = 9 Hz, 1Н), 5.94 (dd, J = 9 Hz, J = 13 Hz, 1Н), 5.85 (dd, J = 8 Hz, J = 13 Hz, 1Н), 5.67 (dd, J = 12 Hz, J = 8 Hz, 1Н), 5.62 (dd, J = 11 Hz, J = 8 Hz, 1Н), 3.71 (dd, J = 6 Hz, J = 9 Hz, 1Н), 2.69-2.74 (m, 1H), 2.66 (d, J = 15 Hz, 1Н), 2.25 (dd, J = 15 Hz, J = 2 Hz, 1Н), 1.94 (d, J = 2 Hz, 3H) ppm. 13С NMR (125 MHz, CDCl3): δ 144.74, 138.20, 137.23, 134.37, 131.34, 128.38 (2C), 128.03 (2C), 126.49, 125.89, 125.83, 123.19, 122.01, 38.35, 38.20, 34.04, 21.78 ppm. MS m/z (EI, 70 eV) m/z (%): 234 [M]+ (46), 204 (32), 191 (19), 178 (18), 143 (82), 129 (75), 115 (55), 105 (62), 91 (100), 77 (36), 51 (18), 41 (4). Anal. Calcd for С18H18: С, 92.26; Н, 7.74. Found: С, 92.11; Н, 7.76.
Tricyclo[9.4.2.02,10]heptadeca-2,12,14,16-tetraene(4): Yield 65%, as pale yellow oil. nd20 1.5341. Rf = 0.52. 1Н NMR (500 MHz, CDCl3): δ 6.06-6.09 (m, 1Н), 5.96–6.00 (m, 1Н), 5.82–5.86 (m, 1Н), 5.76 (dd, J = 8 Hz, J = 12 Hz, 1Н), 5.65–5.70 (m, 2Н), 5.17–5.19 (m, 1Н), 3.25 (dd, J = 8 Hz, J = 9 Hz, 1Н), 3.01–3.06 (m, 2Н), 2.65 (t, J = 9 Hz, 1Н), 1.89–1.95 (m, 1Н), 1.32–1.61 (m, 10Н) ppm. 13С NMR (125 MHz, CDCl3): δ 143.34, 136.30, 136.06, 128.65, 125.59, 124.31, 122.78, 122.36, 46.07, 42.98, 39.91, 32.92, 30.35, 28.33, 28.06, 27.68, 21.61 ppm. MS m/z (EI, 70 eV) m/z (%): 226 [M]+ (7), 169 (9), 155 (23), 141 (53), 129 (100), 115 (43), 91 (68), 77 (25), 55 (16), 41 (31). Anal. Calcd for С17H22: С, 90.20; Н, 9.80. Found: С, 90.01; Н, 9.77.
References
1. Brandsma, L. Best Synthetic Methods: Acetylenes, Allenes and Cumulenes; Elsevier, Acad. Press, London 2003, 502.
2. Baird, M. S.; Nizovtsev, A. V.; Bolesov, I. G. Terahedron2002, 58, 1581.
9-[(E)pentylidene]bicyclo[4.2.2]deca-2,4,7-triene (2a)
9-[(E)-phenylmethylidene]bicyclo[4.2.2]deca-2,4,7-triene (2b)
9-[(E)-2-phenylethylidene)bicyclo[4.2.2]deca-2,4,7-triene (2c)
9-(diphenylmethylene)bicyclo[4.2.2]deca-2,4,7-triene (2d)
9-[(E)-1-phenylethylidene)bicyclo[4.2.2]deca-2,4,7-triene (2e)
Tricyclo[9.4.2.02,10]heptadeca-2,12,14,16-tetraene(4)
Bisadducts 5