3. Hz, 08 (s, 1H), 6.99 (d, J = 8.7 Hz, 2H), 3.85 (s, 3H), 2.39 (s, 3H), C NMR (75 MHz, CDCl 3 ) ? (ppm) 159.9 (C), pp.31-38

2. Hz, 89 (s, 3H); 13 C NMR (75 MHz, CDCl 3 ) ? (ppm) 159 (E)-4-(1-(4-methoxybenzilidene)-1H-inden-3- yl)benzonitrile (3g) The crude residue was purified by flash chromatography on silica gel24 mmol; yield 81%); yellow oil, 120.5 (CH), 119.5 (CH)

2. Hz, 88 (s, 3H) CDCl 3 ) ? (ppm) 160.5 (C), C NMR (75 MHz2CH), 132.1 (2CH), 130.3 (CH), pp.3-55

2. Hz, 13 C NMR (75 MHz, CDCl 3 ) ? (ppm) 160trimethoxyphenyl)-1H-inden-1- ylidene)methyl)benzo-nitrile (3j). The crude residue was purified by flash chromatography on silica gel (Cyclohexane/EtOAc 95/5) to give 80 mg of 3j (0.23 mmol; yield 76%); yellow oil, 2CH), 131.7 (C), 129.9 (C), 128.4 (CH), 127.1 (CH) HRMS (ESI) (M + H) + m IR (film, pp.919493-61, 1007.

. Mhz, 88 (s, 2H), 3.93 (s, 6H), 3.92 (s, 3H); 13 C NMR (75 MHz, CDCl 3 ) ? (ppm) 153, 2H), 6.94 (d, J = 0.6 Hz, 1H) 141.8 (C), 141.1 (C) HRMS (ESI) (M + Na) + m, pp.79-86

A. M. Jiménez-núñez, N. Echavarren, V. Chernyak, A. Gevorgyan, . Synth et al., For more details on the Au-or Pd-catalyzed cyclization of the enyne 1a, see the Supporting Informations. [15] PPh 3 AuNTf 2 is a commercial and air stable gold complex, for synthesis of this complex Electronic effects on cycloisomerization reaction play a critical role on the 5-endo-dig and 6-exo- dig products distribution, see reference 7b. [18] It was assumed that the geometry of all geometrically pure products was the same as that for 3a and 3i, the geometry of which was confirmed by NOESY experiments. [19] Under Pd-conditions, when enyne 1-((4- methoxyphenyl)ethynyl)-2-(prop-1-en-2- yl)benzene was used, a complete recovery of the starting material was observed. The same result is obtained when we tried the cyclization with 1- (hept-1-yn)-2-(1-phenylvinyl)benzene, [21] Heating an isolated E/Z mixture of 3a dioxane at 150 °C for 5 h furnished 3a exclusively as a single E-isomer. [22] For more details, see the Supporting Informations, pp.3326-3350, 1976.

J. V. Foresman, J. Ortiz, D. J. Cioslowski, . Fox, C. C. Wallingford et al., Gaussian 09, revision B.01 [26] For recent examples, see a), Phys. Rev. B J. Chem. Phys. The Journal of Chemical Physics J. Chem. Phys. Org. Lett, vol.37, issue.32, pp.785-789, 1985.

C. J. Roesle, H. M. Dürr, L. Möller, L. Cavallo, S. Caporaso et al., Mechanistic Features of Isomerizing Alkoxycarbonylation of Methyl Oleate, Journal of the American Chemical Society, vol.134, issue.42, pp.17696-17703, 2008.
DOI : 10.1021/ja307411p