Development of Novel Transformation on Polynuclear Transition Metal Complexes

我们已经开发出仅由多核过渡金属配合物（如杂原子桥接的二钌配合物）促进的新转变。我们新发现了以下三个主题。(1)我们已经发现了芳香化合物如N，N-二甲基苯胺，2-甲基呋喃和N-取代吲哚与丙炔醇的对映选择性丙基化反应，由带有光学活性硫酸盐配体的硫代桥接的二钌配合物催化，得到相应的丙基化芳香化合物，收率高，对映选择性高（高达94% ee）。(2)我们发现了双阳离子硫代醇桥接钌配合物催化丙炔醇与丙酮之间的新反应，得到了相应的中至高产率的己二烯酮，这与中性或单阳离子钌配合物作为催化剂生成γ-酮炔形成了鲜明对比。(3)新制备了磷桥接的二钌配合物，并研究了其对丙炔醇与芳香族化合物反应的催化活性，以中等产率生成相应的α，β-不饱和酮。此外，我们还开发了一些新的由硫代酸桥接的二钌配合物催化的反应，如通过丁三烯配合物作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.