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Aryl anion addition to benzonitriles, benzamides, and Vilsmeier-type benzimidoyl chlorides were similarly unsuccessful.
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The synthesis of 15 will be described in a future publication.
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43
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0344671540
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note
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O-Acylation of the nitrilium species blocks unwanted reactions and enhances electrophilicity. It should be noted that entry 5 was carried out with a 2.5-fold excess of the nucleophile to increase the rate of reaction and the net yield. At 1:1 stoichiometry we found that prolonged exposure of this nitrilium salt, and possibly the imine product 19, to the acidic reaction conditions caused removal of the pivaloate ester and side reactions initiated by that unprotected phenol.
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1H NMR spectral assignments we report for OMST 5 are a correction of the original literature and have been verified by NOE experiments conducted on analogous xanthones.
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