Studies on the preparation of novel caged dienes (PCTD) and their derivatices

Bicyclo[2.2.1] Hepta-2，5-diene（2，5-诺本亚丁）Ru催化量的存在的二聚氰胺（1至2）5- 6-η-cyclooctadiene）（1- 6-η-cyclooctatriene）（Ru（cod）（cot）） and an electron-deficient olefin such as N， N-dimethylacrylamide，dimethylfumarate or dimethylmaleate in toluene or THF to give a new compound， pentacyclo[6.6.0.0.0-D12，6-D1.0-D13，13型D1.0型D110，14型D1] tetradeca-4，11-diene（PCTD）， in high yield along with a small amount of a known endo-endo dimer， heptacyclo[6.6.0.0型D12，6型D1.0型D13，13型D1.0型D14，11型D1.0型D15，9型D110，14型D1型D1]tetradecane （HCTD），什么是DMSO中反应中的主要产品？Ru（cod）（cot）-二甲基氟酸THF是最有效的催化剂，PCTD的产量在40 ° C时达到96%。结构of PCTD was directly determined by X-ray analysis of its derivative， [AgOTf（PCTD）] PCTD被发现是通过2，5-北硼二烯的内内-内二烯衍生出来的。PCTD由两个分子组成的2，5-北苯二烯进入清洁剂 ... More 两个碳-碳键的笼子。7-叔丁基-2，5-正硼二烯的尺寸使相应的外-和endo-4，9-不平衡的PCTD衍生物。Ru（cod）（cot） reacts with dimethyl fumarate to give a novel complex， Ru（cod）（dmfm）イイD22イエD2（dmfm=dimethyl fumarate）， in high y\。复合体的结构也是由X射线分析确定的。在40℃在toluene， Ru（cod）（dmfm）D22，D2自身催化量的2，5-norbornadiene在优秀的yield中给予PCTD，使PCTD的大尺度合成（ca.）。（20g）在所有发现的情况下，PCTD形成的可能机制在细节中被讨论。准备各种新颖的笼状化合物，从PCTD衍生出来，可以预期为功能较高的单体，以及对PCTD形成的后续氧化反应进行测试。用氢过氧化物催化剂催化的甲基三氧化物选择性地在高剂量下给予外氧化物，外氧化物的PCTD氧化。Osmium tetraoxide catalyzed selective syn-exo-tetrahydroxylation or syn-exo-dihydroxylation of PCTD with N-methylmorphorine N-oxide。Ruthenium trichloride-催化olefinic group中的氧化清除剂，PCTD与钠periodate gave a derivative of tricyclodecanecarboxylic acid with两个乳糖环。Less（低）

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(cod)(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[6.6.0.0ィイD12,6ィエD1.0ィイD13,13ィエD1.0ィイD110,14ィエD1] tetradeca-4,11-diene (PCTD), in high yield along with a small amount of a known endo-endo dimer, heptacyclo[6.6.0.0ィイD12,6ィエD1.0ィイD13,13ィエD1.0ィイD14,11ィエD1.0ィイD15,9ィエD1.0ィイD110,14ィエD1]tetradecane (HCTD), which is a major product in the reaction in DMSO. Ru(cod)(cot)-dimethyl fumarate in THF was the most efficient catalyst, and the yield of PCTD was 96% even at 40℃. The structure of PCTD was directly determined by X-ray analysis of its derivative, [AgOTf(PCTD)]ィイD2nィエD2. PCTD was found to be derived via endo-endo dimerization of 2,5-norbornadiene. Formation of PCTD from two molecules of 2,5-norbornadiene involves the clea … More vage of two carbon-carbon bonds. Dimerization of 7-tert-butoxy-2,5-norbornadiene gave the corresponding exo- and endo-4,9-disubstituted PCTD derivatives. Ru(cod)(cot) reacts with dimethyl fumarate to give a novel complex, Ru(cod)(dmfm)ィイD22ィエD2(dmfm=dimethyl fumarate), in high yield. The structure of the complex was also determined by X-ray analysis. At 40℃ in toluene, Ru(cod)(dmfm)ィイD22ィエD2 itself catalyzes the dimerization of 2,5-norbornadiene 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. Less