Department Chemie, Technische Universität München, 85748 Garching b. München, Germany.
J Org Chem. 2011 Nov 18;76(22):9353-61. doi: 10.1021/jo201631x. Epub 2011 Oct 19.
The generation of a hidden Brønsted acid as a true catalytic species in hydroalkoxylation reactions from metal precatalysts has been clarified in case studies. The mechanism of triflic acid (CF(3)SO(3)H or HOTf) generation starting either from AgOTf in 1,2-dichloroethane (DCE) or from a Cp*RuCl(2)/AgOTf/phosphane combination in toluene has been elucidated. The deliberate and controlled generation of HOTf from AgOTf and cocatalytic amounts of tert-butyl chloride in the cold or from AgOTf in DCE at elevated temperatures results in a hidden Brønsted acid catalyst useful for mechanistic control experiments or for synthetic applications.
在案例研究中，已经阐明了在氢烷氧基化反应中，金属前催化剂产生隐藏的布朗斯台德酸作为真正的催化物种。从 AgOTf 在 1,2-二氯乙烷（DCE）中或从 Cp*RuCl2/AgOTf/膦组合在甲苯中开始生成三氟甲磺酸（CF3SO3H 或 HOTf）的机制已经阐明。通过故意和受控地从 AgOTf 和催化量的叔丁基氯在低温下或从 AgOTf 在 DCE 中在高温下生成 HOTf，得到了一种有用的隐藏布朗斯台德酸催化剂，可用于机理控制实验或合成应用。
