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For metal-catalyzed approaches to other isoquinoline derivatives, see (selected examples) for Pd: (a) Ban, Y.; Wakamatsu, T.; Mori, M. Heterocycles 1977, 6, 1711.
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For Au: (m) Youn, S. W. J. Org. Chem. 2006, 71, 2521.
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For metal-catalyzed tandem cyclization-addition of 2-alkynyl benzaldimines, see for Ag: (a) Ding, Q.; Ye, Y.; Fan, R.; Wu, J. J. Org. Chem. 2007, 72, 5439.
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For Cu/Zn: (c) Gao, K.; Wu, J. J. Org. Chem. 2007, 72, 8611.
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For In: (d) Yanada, R.; Obika, S.; Kono, H.; Takemoto, Y. Angew. Chem. Int. Ed. 2006, 45, 3822.
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Without catalyst: (e) Asao, N.; Iso, K.; Yudha, S. S. Org. Lett. 2006, 8, 4149.
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Thermal cyclization: (c) Kanekiyo, N.; Kuwada, T.; Choshi, T.; Nobuhiro, J.; Hibino, S. J. Org. Chem. 2001, 66, 8793.
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51
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2, a slow decomposition was observed but none of the isoquinoline-N-oxide was observed in this case.
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2, a slow decomposition was observed but none of the isoquinoline-N-oxide was observed in this case.
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52
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0000931050
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Representative Preparatory Procedure for Isoquinoline N-oxide 2a (Method B) To a solution of oxime 1a (20 mg, 0.090 mmol) in CH2Cl2 (1 mL) was added AgOTf (1.2 mg, 0.0045 mmol) and the mixture was stirred at r.t. for 30 min. The solvent was removed and the residue was purified by silica gel chromatography (CH 2Cl2-MeOH, 10:1) to give 17.0 mg (85, of 2a as a white solid (method A, To a mixture of Au(IMeS)Cl (5 mol, and AgOTf (5 mol, in CH2Cl2 (ca. 0.1 M) at r.t. was added substrate. Otherwise, a similar procedure to method B was followed. Compound 2a: 1H NMR (400 MHz, CDCl3, δ, 8.91 (s, 1 H, 7.93-7.76 (m, 4 H, 7.76-7.67 (m, 1 H, 7.67-7.54 (m, 2 H, 7.54-7.38 (m, 3 H, 13C NMR 100 MHz, CDCl3, δ, 147.8, 137.7, 133.5, 130.4, 130.1, 129.9, 129.74, 129.70, 129.5, 128.9, 127.3, 125.5, 125.1. HRMS: m/z calcd for
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3): δ = 157.6, 137.3, 134.8, 132.1, 129.4, 128.5, 127.5, 125.8, 122.9, 116.7, 38.1, 32.6, 23.0, 14.5.
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