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The reaction of tryptamine with ethylformate gives a formamide, which when treated with NaH and allyl bromide gives a mixture of 1, 2, and 3. With a careful selection of the reaction conditions mono- or diallyl products can become major products selectively. Compound 5 was obtained by reaction with excess propargyl bromide. See Supplementary data for details.
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31
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62849083783
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note
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Alternatively to the synthesis of 6a and 6b from 1, as this starting material is obtained in low yield, dihydro-β-carboline was protected as the tosyl derivative, and reacted with an alkynylmagnesium bromide. The resulting 1-ethynyl or 1-(1-propynyl)-9-tosyltetrahydro-β-carboline was allylated giving 6a and 6b in a global yield of 42 and 49%, respectively.
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62849102550
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Although it was generally accepted that enyne metathesis reactions follow an yne-ene pathway involving initial coordination of the alkyne to the metal, there is actually evidence for an ene-yne pathway, see: and references cited therein
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Although it was generally accepted that enyne metathesis reactions follow an yne-ene pathway involving initial coordination of the alkyne to the metal, there is actually evidence for an ene-yne pathway, see:. Sohn J.H., Kim K.H., Lee H.Y., No Z.S., and Ihee H. J. Am. Chem. Soc. 130 (2008) 16506-16507 and references cited therein
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These kinds of oxidations have been used for the synthesis of aromatic compounds. See:
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4, following a procedure described in: Unfortunately we observed no reaction after 3 days, recovering the starting material unchanged
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4, following a procedure described in:. Yang Q., Xiao W.J., and Yu Z. Org. Lett. 7 (2005) 871-874 Unfortunately we observed no reaction after 3 days, recovering the starting material unchanged
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62849109860
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note
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2. This reaction gave a mixture of 15a, 37a, 35a, and 35b, in the following ratios (2:3:2:1). From this mixture, 15a (10%), 37a (27%), and 35a (13%) were isolated.
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44
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4544222031
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