Organometallic gold(III) compounds as catalysts for the addition of water and methanol to terminal alkynes
Organometallic gold(III) compounds as catalysts for the addition of water and methanol to terminal alkynes
复制标题
DOI：
10.1021/ja036049x
复制
发表时间：
2003-10-01
影响因子：
15
通讯作者：
Sanz, S
中科院分区：
文献类型：
--
作者：
Casado, R;Contel, M;Sanz, S
不同的无机和有机金属金（III）和金（I）配合物已被测试在添加水和甲醇的末端炔。阴离子和中性的有机金属金（III）化合物可以有效地介导这些反应在中性介质中的甲醇。化合物以催化量（相对于炔为1.6-4.5摩尔%）加入。因此，通式Q[AuRCl 3]、Q[AuR 2Cl 2]、[AuRCl 2]（2）和[AuR 2Cl]（2）（Q = BzPPh（3）（+），PPN：N（PPh 3）（2+）或N（Bu）（4）（+）; R = C6 F5或2，4，6-（CH 3）（3）C6 H2）的化合物似乎表现为与三键亲核加成的刘易斯酸。在[Au（C6 F5）（2）Cl]（2）与苯乙炔的化学计量反应中，通过变温H-1、F-19{H-1}、COSY F-19 {H-1}-F-19 {H-1}和H-2{H-1} NMR实验，可以检测到一些中间体。化合物[Au（C6 F5）（2）Cl]（2）在室温下也能催化苯乙炔的水合反应。一个合理的水合反应的机制已被提出。
Different inorganic and organometallic gold(Ill) and gold(l) complexes have been tested in the addition of water and methanol to terminal alkynes. Anionic and neutral organometallic gold(Ill) compounds can efficiently mediate these reactions in neutral media in refluxing methanol. The compounds are added in catalytic amounts (1.6-4.5 mol % with respect to the alkyne). Thus, compounds of the general formula Q[AuRCl3], Q[AuR2Cl2], [AuRCl2](2), and [AuR2Cl](2) (Q = BzPPh(3)(+), PPN: N(PPh3)(2+) or N(Bu)(4)(+); R = C6F5 or 2,4,6-(CH3)(3)C6H2) seem to behave as Lewis acids in nucleophilic additions to triple bonds. Some intermediates could be detected in the stoichiometric reaction between [Au(C6F5)(2)Cl](2) and phenylacetylene that was followed by variable temperature H-1, F-19{H-1}, COSY F-19{H-1}-F-19{H-1}, and H-2{H-1} NMR experiments. Compound [Au(C6F5)(2)Cl](2) is also able to catalyze the hydration of phenylacetylene at room temperature. A plausible mechanism for the hydration reaction has been proposed.