Hidden Bronsted Acid Catalysis: Pathways of Accidental or Deliberate Generation of Triflic Acid from Metal Triflates
Hidden Bronsted Acid Catalysis: Pathways of Accidental or Deliberate Generation of Triflic Acid from Metal Triflates
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DOI：
10.1021/jo201631x
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发表时间：
2011-11-18
影响因子：
3.6
通讯作者：
Hintermann, Lukas
中科院分区：
文献类型：
--
作者：
Tuan Thanh Dang;Boeck, Florian;Hintermann, Lukas
一个隐藏的布朗斯台德酸的产生作为一个真正的催化物种在加氢烷氧基化反应从金属预催化剂已澄清的案例研究。三氟甲磺酸（CF_3SO_3H或HOTf）的生成机理可以从AgOTf在1，2-二氯乙烷（DCE）中的溶液或从Cp* RuCl_2/AgOTf/膦在甲苯中的溶液中的混合物中得到阐明。在低温下由AgOTf和助催化量的叔丁基氯或在升高的温度下由DCE中的AgOTf有意和受控地生成HOTf导致可用于机械控制实验或合成应用的隐藏的布朗斯台德酸催化剂。
The generation of a hidden Bronsted acid as a true catalytic species in hydroalkoxylation reactions from metal precatalysts has been clarified in case studies. The mechanism of triflic acid (CF3SO3H or HOTf) generation starting either from AgOTf in 1,2-dichloroethane (DCE) or from a Cp*RuCl2/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 Bronsted acid catalyst useful for mechanistic control experiments or for synthetic applications.