Inada Youichi, Nishibayashi Yoshiaki, Hidai Masanobu, Uemura Sakae
Department of Energy and Hydrocarbon Chemistry, Kyoto University, Sakyo-ku, Kyoto 606-8501, Japan.
J Am Chem Soc. 2002 Dec 25;124(51):15172-3. doi: 10.1021/ja027754t.
A novel cationic methanethiolate-bridged diruthenium complex [CpRuCl(mu2-SMe)2RuCp(OH2)]OTf (1e) has been disclosed to promote the catalytic propargylic substitution reaction of propargylic alcohols bearing not only terminal alkyne group but also internal alkyne group with thiols. It is noteworthy that neutral thiolate-bridged diruthenium complexes (1a-1c), which were known to promote the propargylic substitution reactions of propargylic alcohols bearing a terminal alkyne group with various heteroatom- and carbon-centered nucleophiles, did not work at all. The catalytic reaction described here provides a general and environmentally friendly preparative method for propargylic sulfides, which are quite useful intermediates in organic synthesis, directly from the corresponding propargylic alcohols and thiols.
一种新型的阳离子甲硫醇盐桥联二钌配合物[CpRuCl(μ2-SMe)2RuCp(OH2)]OTf (1e)已被公开，可促进不仅带有末端炔基而且带有内炔基的炔丙醇与硫醇的催化炔丙基取代反应。值得注意的是，已知能促进带有末端炔基的炔丙醇与各种以杂原子和碳为中心的亲核试剂发生炔丙基取代反应的中性硫醇盐桥联二钌配合物(1a - 1c)根本不起作用。这里描述的催化反应为炔丙基硫醚提供了一种通用且环境友好的制备方法，炔丙基硫醚是有机合成中非常有用的中间体，可直接由相应的炔丙醇和硫醇制备。
