Synthesis of Trithiolanes and Tetrathianes from Thiiranes Catalyzed by Ruthenium Salen Nitrosyl Complexes
作者:Anthony A. Sauve、John T. Groves
DOI:10.1021/ja017462c
日期:2002.5.1
solution thiirane behaves as a sulfur donor and forms olefin, whereas the coordinated thiirane becomes the cyclic polysulfide. beta-cis-Deuteriostyrene sulfide was used to show that ring closure to form cyclic polysulfide incorporated inversion of stereochemistry versus starting thiirane. A mechanism for catalysis consistent with experimental data is presented that requires coordination of thiirane to the
化合物 [Ru(salen)(NO)(H(2)O)](SbF(6)) (1)(salen = N,N'-亚乙基-双-水杨基胺)与硫杂丙烷催化反应并将它们转化为烯烃和 1,2,3,4-四硫杂环烷或 1,2,3-三硫杂环戊烷。单取代硫杂丙环硫醚和硫化丙烯反应生成相应的烯烃和 4-取代的 1,2,3-三硫杂环戊烷,其比例为 2:1,分离产率超过 90%。在催化量 1 的 CD(3)NO 存在下,二取代硫杂丙烷顺式二苯乙烯硫醚以 3:1 的比例转化为顺式二苯乙烯和 5,6-反式-1,2,3,4-二苯基四硫烷(2). 通过分离 [Ru(salen)(NO)(cis-stilbene sulfide)](SbF(6)) (6),建立了在配体取代反应中顺式二苯乙烯硫化物与 salen 复合物的协调。(1) 对 6 进行的 H NMR 研究表明,salen 大环已在硫杂环丙烷配位后重新排列。发现类似的重排