Novel Organic Syntheses by Reconstruction of Carbon Skeletons via Catalytic Carbon-Carbon Bond Cleavage

双环[2.2.1]庚-2，5-二烯在催化量的Ru存在下，（1-2：5-6-η-环辛烯）（1-6-η-环辛三烯）（Ru（η^4-cod）（η^6-cot））和缺电子烯烃如N，N-二甲基丙烯酰胺、富马酸二甲酯或马来酸二甲酯在甲苯或THF中反应，得到新化合物，五环[6.6.0^<2，6>.0^<3，13>.0^<10，14>]十四碳-4，11-二烯（PCTD）。通过对PCTD衍生物[AgOTf（PCTD）]_n的X射线衍射分析，直接确定了PCTD的结构。发现PCTD经由2，5-降冰片二烯的内-内二聚化衍生。由两个2，5-降冰片二烯分子形成PCTD涉及两个碳-碳键的断裂。Ru（η^4-cod）（η^6-cot）与富马酸二甲酯反应，高产率地合成了一种新的配合物Ru（1-6-η-环辛三烯）（η^2-富马酸二甲酯）_2。配合物的结构也通过X-射线衍射分析确定。在甲苯中，40 ℃时Ru（η^6-cot）（η^2-dmfm）_2本身催化2，5-norb的二聚反应 ...更多信息 在不存在烯属添加剂的情况下，通过使用降冰片二烯以优异的产率得到PCTD，这使得能够大规模合成PCTD（ca. 20 g）。考虑到所有的发现，PCTD的形成的可能机制进行了详细讨论。为了制备各种新的笼状化合物，从PCTD，这可以预期作为高功能单体，以下PCTD的氧化反应进行了研究。以甲基三氧化铼为催化剂，过氧化氢氧化PCTD，高收率地选择性地得到外，外-二环氧化物。四氧化锇催化PCTD与N-甲基吗啉N-氧化物的顺-外-四羟基化或顺-外-二羟基化反应。三氯化钌催化高碘酸钠氧化裂解PCTD中的烯基，得到了一种具有两个内酯环的三环癸烷羧酸衍生物。（η^2-dmfm）_2，它很容易由Ru（η^4-cod）（η^6-cot）制备，与单齿或双齿胺和膦配体顺利反应得到各种相应的新型钌（0）胺和膦配合物，可以预期其对碳-碳键形成反应以及碳-碳键断裂反应具有高催化活性。少

Bicyclo[2.2.1]hepta-2, 5-diene(2, 5-norbornadiene)dimerizes in the presence of a catalytic amount of Ru(1-2 : 5-6-η-cyclooctadiene)(1-6-η-cyclooctatriene)(Ru(η^4-cod)(η^6-cot))and an electron-deficient olefin such as N, N-dimethylacrylamide, dimethyl fumarate or dimethyl maleate in toluene or THF to give a new compound, pentacyclo[6.6.0^<2,6>.0^<3,13>.0^<10,14>]tetradeca-4, 11-diene(PCTD), in excellent yield. The structure of PCTD was directly determined by X-ray analysis of its derivative, [AgOTf(PCTD)]_n. PCTD was found to be derived via endo-endo dimerization of 2, 5-norbornadiene. Formation of PCTD from two molecules of 2, 5-norbomadiene involves the cleavage of two carbon-carbon bonds. Ru(η^4-cod)(η^6-cot)reacts with dimethyl fumarate to give a novel complex, Ru(1-6-η-cyclooctatriene)(η^2-dimethyl fumarate)_2, in high yield. The structure of the complex was also determined by X-ray analysis. At 40 ℃ in toluene, Ru(η^6-cot)(η^2-dmfm)_2 itself catalyzes the dimerization of 2, 5-norb … More ornadiene to give PCTD in excellent yield in the absence of olefinic additives, which enabled the large scale synthesis of PCTD(ca. 20 g). In consideration of all findings, the possible mechanisms of the formation of PCTD are discussed in detail.To prepare various novel caged compounds, derived from PCTD, which can be expected as highly functional monomers, the following oxidation reactions of PCTD were examined. Oxidation of PCTD with hydrogen peroxide catalyzed by methyltrioxorhenium selectively gave the exo, exo-diepoxide in high yield. Osmium tetraoxide catalyzed selective syn-exo-tetrahydroxylation or syn-exo-dihydroxylation of PCTD with N-methylmorphorine N-oxide. Ruthenium trichloride-catalyzed oxidative cleavage of the olefinic groups in PCTD with sodium periodate gave a derivative of tricyclodecanecarboxylic acid with two lactone rings.Finally, we found that Ru(η^6-cot)(η^2-dmfm)_2, which is easily prepared from Ru(η^4-cod)(η^6-cot), smoothly reacts with monodentate or bidentate amine and phosphine ligands to give a variety of the corresponding novel ruthenium(0)amine and phosphine complexes, which can be expected to have high catalytic activities toward carbon-carbon bond forming reactions as well as carbon-carbon bond cleavage reactions. Less