Construction of Phthalocyanine-Based Solid Phase Tags and Their Utility for Synthetic Organic Chemistry

酞菁基固相标签的构建及其在有机合成化学中的应用

基本信息

批准号：
17590018
负责人：
TAKANAMI Toshikatsu
金额：
$ 2.44万
依托单位：
Meiji Pharmaceutical University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
2005
资助国家：
日本
起止时间：
2005 至 2007
项目状态：
已结题

项目摘要

A broad range of topics of porphyrin and phthalocyanine chemistry including construction of phthalocyanine-based solid phase tags were studied. The results obtained are summarized as follows.1. A metallophthalocyanine complex, Cr(TBPC) OTf works as an efficient Lewis acid catalyst that can promote the regio- and stereoselective rearrangement of epoxides to aldehydes. It shows not only high efficiencies in yields and selectivities, but also excellent reusability, in the catalysis, which enables practical synthesis of enantio-enriched aldehydes bearing a stereogenic quatemary carbon center from optically active tri-substituted epoxides.2 The catalytic Z-selective Claisen rearrangement of simple aliphatic allyl vinyl ethers can be realized using a chromium(III) porphyrin complex, Cr(IPP) C1, as a catalyst Cr(TPP) Cl significantly enhances reversal of E/Z selectivity in the thermal Claisen rearrangement of allyl vinyl ethers at low catalyst loading3. We have developed the first method that … More achieves catalytic mono-and dicyanation of porphyrins. These palladium-catalyzed cyanation reactions utilizing cyanoethyl zinc bromide as an efficient cyanide ion source are compatible with an array of porphyrins.4. A simple one-pot procedure that converts 5, 15-substituted porphyrins into the corresponding meso formylated porphyrins has been developed. The method, based on a new synthetic concept for functionalized porphyrins utilizing the(2-pyridyl-dimethylsilyl) methyl group as a latent formyl functionality, affords desired product in good yield.5. A series of mono-and bis-functionalized meso-substituted porphyrins bearing chemically reactive functional groups in the alkyl substituents at the meso positions were efficiently synthesized by the reactions of meso-brominated precursors with alkylzinc reagents via palladium-catalyzed Negishi cross-coupling.6. A new supramolecular chirogenic system on the basis of zinc porphyrin dimers and various enantiopure organic molecules, which was specifically designed for investigation of the chirogenic phenomenon upon extremely weak interaction modes and marginal chiroptical responses, is studied. Less

研究了多种卟啉和邻苯丙氨酸化学的主题，包括构建基于邻苯二苯胺的固相标签。获得的结果总结如下1。一种金属果心氨基酸酯络合物CR（TBPC）OTF充当有效的路易斯酸催化剂，可以促进环氧化物对醛的区域和立体选择性重排。 It shows not only high efficiency in yields and selectivities, but also excellent Reusability, in the catalysis, which enables practical synthesis of enantio-enriched aldehydes bearing a stereogenic quantumary carbon center from optically active tri-substituted epoxides.2 The catalytic Z-selective Claisen rearrangement of simple aliphatic allyl vinyl ethers can be realized using a作为催化剂CR（TPP）CL的铬（III）卟啉复合物CR（IPP）C1显着增强了在低催化剂载荷下烯丙基乙烯基醚的热claisen重排中E/Z选择性的逆转3。我们开发了第一种方法，该方法……更多地实现了卟啉的催化单和词典。这些利用氰基锌作为有效的氰化物离子源的钯催化的氰化反应与卟啉阵列兼容。4。已经开发了一种简单的单盘程序，该程序将5个，15个取代的卟啉转化为相应的Meso配方卟啉。该方法基于使用（2-吡啶基二甲基甲硅烷基）甲基作为潜在甲基功能的新型合成概念，用于官能化的卟啉，可提供良好产量的所需产品。5。在中索位置，在烷基替代物中具有化学反应性官能团的一系列单单和双官能化的中型卟啉有效地通过了中溴溴化的前体与烷基基因试剂通过钯催化的核糖含量的negishiishi Crossishi crossing.6的反应有效地合成。根据极弱的相互作用模式和边缘芯片反应的极弱，是专门设计的，它是根据锌卟啉二聚体和各种对映体有机分子的新的超分子性手化系统的。