Department of Chemistry and Applied Chemistry, Graduate School of Science and Engineering, Saga University , Honjo-machi, Saga 840-8502, Japan.
Org Lett. 2015 Oct 2;17(19):4778-81. doi: 10.1021/acs.orglett.5b02336.
A strategy for desilylative acetoxylation of (trimethylsilyl)arenes has been developed in which (trimethylsilyl)arenes are converted into acetoxyarenes. The direct acetoxylation is performed in the presence of 5 mol % of Pd(OAc)2 and PhI(OCOCF3)2 (1.5 equiv) in AcOH at 80 °C for 17 h. The acetoxyarenes are obtained in good to high yields (67-98%). The synthetic utility is demonstrated with a one-pot transformation of (trimethylsilyl)arenes to phenols by successive acetoxylation and hydrolysis. Furthermore, desilylative acyloxylation of 2-(trimethylsilyl)naphthalene using several carboxylic acids has been conducted.
已开发出一种将（三甲基硅基）芳基去硅基乙酰氧基化的策略，其中（三甲基硅基）芳基转化为乙酰氧基芳基。在 AcOH 中，在 5 mol% 的 Pd(OAc)2 和 PhI(OCOCF3)2（1.5 当量）的存在下，直接进行乙酰氧基化，在 80°C 下反应 17 小时。乙酰氧基芳基以良好至高收率（67-98%）获得。通过连续的乙酰氧基化和水解，一锅法将（三甲基硅基）芳基转化为苯酚，展示了其合成实用性。此外，还进行了使用几种羧酸的 2-（三甲基硅基）萘的去硅基酰氧基化。
