Organotin perfluorooctanesulfonates as air-stable Lewis acid catalysts: Synthesis, characterization, and catalysis
Organotin perfluorooctanesulfonates as air-stable Lewis acid catalysts: Synthesis, characterization, and catalysis
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DOI：
10.1002/chem.200501091
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发表时间：
2006-02-08
影响因子：
4.3
通讯作者：
Otera, J
中科院分区：
文献类型：
--
作者：
An, DL;Peng, ZH;Otera, J
1，3-二氯-1，1，3，3-四丁基二锡氧烷和二烷基锡二卤化物与全氟辛烷磺酸银反应，得到相应的磺酸盐水合物。水合的水分子数（n）取决于条件。二锡氧烷衍生物被确定为n从0.5至6，而在水合单核物种和DMSO复合物n变化很大，从4至13。Sn-119 NMR光谱和电导率测量表明这些化合物在溶液中的离子解离。这些化合物在极性有机溶剂中表现出异常高的溶解度。离子解离和水化作用可能是导致这种不寻常溶解度的原因。超氧化物/金属离子络合物的ESR谱的基础上，这些化合物的刘易斯酸性被发现是高的有机锡衍生物。与公知的有机锡三氟甲磺酸盐相反，这些化合物在露天储存时不发生水解。二锡氧烷1的高催化活性被例示用于各种碳-碳键形成反应，如Mukaiyama-羟醛缩合以及-Michael反应和醛的烯丙基化。
The reactions of 1,3-dichloro-1,1,3,3-tetrabutyldistannoxane and di-alkyltin dihalides with silver perfluoro-octanesulfonate provided the corresponding sulfonates as hydrates. The number of water molecules (n) of hydration was dependent on the conditions. The distannoxane derivative was identified as n from 0.5 to 6, while in the hydrated mononuclear species and DMSO complexes n varied widely from 4 to 13. Sn-119 NMR spectroscopy and conductivity measurements indicated the ionic dissociation of these compounds in solution. These compounds exhibited unusually high solubility in polar organic solvents. The ionic dissociation together with facile hydration probably causes the unusual solubility. The Lewis acidity of these compounds was found to be high among organotin derivatives on the basis of ESR spectra of superoxide/ metal-ion complexes. In contrast to well-known organotin triflates, these compounds suffered no hydrolysis upon storage in open air. The high catalytic activity of the distannoxane 1 was exemplified for various carbon-carbon bond-forming reactions, such as Mukaiyama-aldol as well as -Michael reactions and allylation of aldehydes.