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

点击翻译按钮获取中文摘要

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