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

研究了一系列关于卟啉和酞菁化学的主题，包括构建基于酞菁的固相标记物。所获得的结果概括如下：1.金属酞菁配合物铬(TBPC)OTF是一种高效的Lewis酸催化剂，能促进环氧化物的区域和立体选择性重排反应生成醛。它不仅表现出高的产率和选择性，而且在催化中具有良好的重复使用性，使得从光学活性的三取代环氧化物中实际合成具有立体生成的四元碳中心的富含对映体的醛成为可能。2简单的脂肪族烯丙基醚的Z选择性Claisen重排可以用铬(III)卟啉络合物Cr(IPP)C_1作为催化剂在低催化剂载量下显著提高E/Z选择性的逆转。我们已经开发出第一种方法，即…更多的实现了卟啉的催化单氰化和双氰化。这些钯催化的氰化反应使用氰乙基溴化锌作为有效的氰离子来源，与一系列的卟啉是相容的。建立了一种简单的一锅法将5，15-取代的卟啉转化为相应的中甲酰化卟啉的方法。该方法基于一种利用(2-吡啶-二甲基硅基)甲基作为潜在的甲酰基官能团的官能化卟啉的新合成概念，以良好的产率提供了所需的产物。通过中溴前驱体与烷基锌试剂通过钯催化的Negishi交叉偶联反应，有效地合成了一系列单官能化和双官能化的中位取代卟啉。研究了一种基于锌卟啉二聚体和各种对映体有机分子的超分子手性反应体系，该体系是专门为研究极弱相互作用模式和边缘手性反应时的手性现象而设计的。较少

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