Construction of Novel Chiral Host Molecule Systems Utilizing meso-Carbon Bridged Porphyrin Dimers and Their Application to Organic Synthesis

研究了广泛的卟啉化学主题，包括利用中碳桥联的卟啉二聚体构建新颖的和合成上有用的手性主体分子体系。主要研究结果如下：(1)高价金属卟啉配合物铬(TPP)OTF在较低的催化剂负载量下，可以很容易地实现环氧化物的烷基迁移催化重排和区域及立体选择性重排为醛。由于我们以前已经报道过Fe(Tpp)X催化环氧化物通过氢化重排成酮，因此，通过简单地选择Fe(III)和Cr(III)作为卟啉催化剂的中心金属离子，可以以高度可控的方式从环氧化物中选择性地制备酮和醛。(2)现在可以实现一种新颖而高效的可回收催化剂体系，该催化剂体系是以酞菁为基础的路易斯酸催化剂，能够有效地促进环氧化物的区域和立体选择性重排，以制备Ald…更多的赞美诗。这种可回收的催化剂体系为从环氧化物合成光学活性醛提供了一种操作简单、实用的方法。(3)基于卟啉的Lewis酸催化剂可以通过协同的[3，3]途径有效地加速重排反应，底物的键电离程度最小，在低催化剂负载量下以中高产率和几乎完全的区域选择性提供相应的Claisen产物。该催化体系最显著的优点是其独特的立体选择性：在烯丙基乙烯基醚，特别是4，5-和4，6-二取代衍生物的热Claisen重排反应中，铬(TPP)氯能显著提高E/Z选择性的逆转，并以催化的方式进行。(4)钯催化的溴卟啉氰化反应是以氰乙基溴化锌为特定氰化剂实现的。这一新的方案提供了一种容易获得各种氰化锌(II)卟啉的方法，包括中位-单氰基、中位-双氰基和β-单氰基取代的锌(II)配合物。(5)通过卟啉与硅甲基锂试剂，特别是PYMe_2SiCH_2Li的取代反应，然后用DDQ氧化，我们开发了一种简便、高效的中甲酰基取代卟啉的合成方法。(6)采用伪界面构象的卟啉二聚体可以在室温下有效地结合各种有机分子，如胺、醇和醚。我们还公开了基于CD激子手性方法的卟啉二聚体用于手性胺和醇的直接传感。较少

A broad range of topics of porphyrin chemistry including construction of novel and synthetically useful chiral host molecule systems utilizing meso-carbon bridged porphyrin dimers were studied. The results obtained are briefly summarized as follows.(1) Catalytic and regio-and stereoselective rearrangement of epoxides to aldehydes via an alkyl migration can easily be achieved with a high valent metalloporphyrin complex, Cr(tpp)OTf, at a low catalyst loading. Since we have previously reported that Fe(tpp)X catalyzes the rearrangement of epoxides to ketones via a hydrogen mygration, ketones and aldehydes can selectively be prepared from epoxides in a highly controlled manner by the simple choice of Fe(III) and Cr(III) as a central metal ion of the porphyrin catalysts.(2) A novel and efficient recyclable catalyst system can now be realized using a phthalocyanine-based Lewis acid catalyst, Cr(PC)OTf, that can effectively promote the regio-and stereoselective rearrangement of epoxides to ald … More ehydes. This recyclable catalyst system provides an operationally simple, practical way for synthesizing optically active aldehydes from epoxides.(3) The porphyrin-based Lewis acid catalyst can effectively accelerate the rearrangement via a concerted [3,3] pathway with a minimal degree of bond ionization of the substrates, providing the corresponding Claisen products in moderate to high yields and almost perfect regioselectivity at low catalyst loading. The most notable advantage of the catalyst system is its unique stereoselectivity: Cr(TPP)Cl significantly enhances reversal of E/Z selectivity in the thermal Claisen rearrangement of allyl vinyl ethers, especially, 4,5-and 4,6-disubstituted derivatives, and dose so in a catalytic fashion.(4) Palladium-catalyzed cyanation of bromoporphyrins is now realized using cyanoethylzinc bromide as a specific cyanating agent. This new protocol provides an easy access to various cyanated Zn(II) porphyrins, including meso-mono-, meso-di-, and β-mono-cyano-substituted Zn(II) complexes.(5) A facile and efficient synthesis of meso-formyl substituted porphyrins via substitution reactions of porphyrins with silylmethyllithium reagents, especially PyMe2SiCH2Li, followed by oxidation with DDQ has been developed.(6) The porphyrin dimers that adopt a pseudocofacial conformation can effectively bind a variety of organic molecules, such as amines, alcohols, and ethers, over room temperatures. We also disclosed the use of the porphyrin dimers for the direct sensing of chiral amines and alcohols based on the CD exciton chirality method. Less