Department of Chemistry, University College London, Christopher Ingold Laboratories, 20 Gordon Street, London, WC1H 0AJ, UK.
Chemistry. 2012 Apr 10;18(15):4748-58. doi: 10.1002/chem.201102830. Epub 2012 Feb 28.
A wide range of primary, secondary and tertiary propargylic alcohols undergo a Meyer-Schuster rearrangement to give enones at room temperature in the presence of a gold(I) catalyst and small quantities of MeOH or 4-methoxyphenylboronic acid. The syntheses of the enone natural products isoegomaketone and daphenone were achieved using this reaction as the key step. The rearrangement of primary propargylic alcohols can readily be combined in a one-pot procedure with the addition of a nucleophile to the resulting terminal enone, to give β-aryl, β-alkoxy, β-amino or β-sulfido ketones. Propargylic alcohols bearing an adjacent electron-rich aryl group can also undergo silver-catalyzed substitution of the alcohol with oxygen, nitrogen and carbon nucleophiles. This latter reaction was initially observed with a batch of gold catalyst that was probably contaminated with small quantities of silver salt.
各种伯、仲和叔炔丙醇在金（I）催化剂和少量甲醇或 4-甲氧基苯硼酸的存在下，于室温下发生 Meyer-Schuster 重排，生成烯酮。该反应是合成烯酮天然产物异庚酮和达芬酮的关键步骤。伯炔丙醇的重排可以很容易地与亲核试剂的添加结合在一锅法中进行，从而得到β-芳基、β-烷氧基、β-氨基或β-硫代酮。邻位富电子芳基取代的炔丙醇也可以通过银催化与氧、氮和碳亲核试剂进行醇的取代反应。该反应最初是在一批可能被少量银盐污染的金催化剂的情况下观察到的。
