Development of Novel Transformation on Polynuclear Transition Metal Complexes

我们已经开发了仅由多核过渡金属络合物促进的新的转化，例如杂原子桥联的二Ru络合物。我们新发现了以下三个主题。(1)我们发现N，N-二甲基苯胺、2-甲基呋喃和N-取代吲哚等芳香族化合物在含光学活性硫醇配体的硫代桥联二Ru络合物催化下与炔丙醇进行不对称烷基化反应，以较高的产率和较高的对映选择性(最高可达94%ee)得到相应的芳香族化合物。(2)我们发现在阳离子硫醇桥联二Ru络合物的催化下，丙酮和丙酮发生了新的反应，以中等到较好的产率得到相应的己二酮，这与中性或单阳离子二Ru络合物催化生成γ-酮炔形成了鲜明对比。(3)我们合成了新的磷桥联二Ru配合物，并考察了它们对丙叉醇与芳香族化合物反应的催化活性，以中等产率合成了相应的α，β-不饱和酮。此外，我们还开发了一些新型的硫氧桥联二Ru络合物催化的反应，如以丁三烯络合物为关键中间体与亲核试剂的乙烯基取代反应。

We have developed novel transformations only promoted by polynuclear transition metal complexes such as heteroatom-bridged diruthenium complexes. We have newly found the following three topics. (1) We have found enantioselective propargylation of aromatic compounds such as N,N-dimethylanilines, 2-methylfuran, and N-substituted indoles with propargylic alcohols catalyzed by thiolated-bridged diruthenium complexes bearing optically active thiolate ligands to give the corresponding propargylated aromatic compounds in good to high yields with a high enantioselectivity (up to 94% ee). (2) We have found novel reactions between propargylic alcohols and acetone catalyzed by dicationic chalcogenolated-bridged diruthenium complexes to give the corresponding hexadienones in moderate to good yields, in sharp contrast to the formation of γ-ketoalkynes when neutral or monocationic diruthenium complexes are employed as catalysts. (3) We have newly prepared phosphido-bridged diruthenium complexes and investigated their catalytic activity toward reactions of propargylic alcohols with aromatic compounds to give the corresponding α,β-unsaturated ketones in moderate yields. In addition, we have developed novel some reactions catalyzed by thiolate-bridged diruthenium complexes such as vinylic substitution reactions with nucleophiles via butatrienylidene complexes as key intermediates.