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Methyl pyrrole-2-carboxylate was obtained from pyrrole by acylation with trichloroacetyl chloride as described by Harbuck, J. W.; Rapoport, H. J. Org. Chem. 1972, 37, 3618. The 2-trichloroacetylpyrrole was treated with a solution of NaOMe in MeOH at 0 °C to furnish the methyl ester.
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Tosylate 4 was obtained from the 2-bromo-5-isopropoxy-4- methoxybenzaldehyde as detailed in Supporting Information. A Wittig reaction afforded the styrene, while anti-Markovnikov hydroboration and standard tosylation of the resulting 2-(2-bromo-5-isopropoxy-4-methoxyphenyl)ethanol gave 4. Preparation of 2-(2-bromo-5-isopropoxy-4-methoxyphenyl) ethanol was described from the same benzaldehyde using a different procedure by: Treu, M.; Jordis, U. Molecules 2002, 7, 374.
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25444433488
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note
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13C NMR.
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12
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25444433987
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note
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1H NMR. The reaction could be followed by HPLC.
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13
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1842452582
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25444493018
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note
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Obtained from 3-isopropoxy-4-methoxybenzaldehyde by Baeyer-Villiger reaction followed by protection of the resulting phenol and bromination; see Supporting Information for details.
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15
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0001029926
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Kranenburg, M.; van der Burgt, Y. E. M.; Kamer, P. C. J.; van Leeuwn, P. W. N. M.; Goubitz, K. Fraange, J. Organometallics 1995, 14, 3081.
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2 were inefficient for this transformation: Baudoin, O.; Guénard, D.; Guéritte, F. J. Org. Chem. 2000, 65, 9268.
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25444451482
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note
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2 and DPEphos afforded the debrominated compound, 2,4-diisopropoxy-1-methoxybenzene, instead of the desired building block 11b.
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19
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25444480403
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note
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2 in refluxing toluene or pyridine, or (iii) Pd-C in toluene or decalin were unsuccessful (unpublished results).
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20
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0141743523
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Protection of phenol groups as isopropoxyethers was previously demonstrated to be very efficient in the solid-phase synthesis of lamellarins: Cironi, P.; Manzanares, I.; Albericio, F.; Álvarez, M. Org. Lett. 2003, 5, 2959.
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22
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4544233786
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and references therein
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For an example of DTS, see: Gaul, C.; Njadarson, J. T.; Shan, D.; Diorn, D. C.; Wu, K-D.; Tong, W. T.; Huang, X.-Y.; Moore, M. A. S.; Danishefsky, S. J. J. Am. Chem. Soc. 2004, 126, 11326 and references therein.
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