Department of Chemistry , University of Connecticut , Unit 3060, Storrs , Connecticut 06269-3060 , United States.
Department of Chemistry , University of Washington , Box 351700, Seattle , Washington 98195 , United States.
J Org Chem. 2019 Jan 4;84(1):239-256. doi: 10.1021/acs.joc.8b02628. Epub 2018 Dec 18.
Porpholactones are porphyrinoids in which one or more β,β'-bonds of the parent chromophore were replaced by lactone moieties. Accessible to varying degrees by direct and nonselective oxidations of porphyrins, the rational syntheses of all five dilactone isomers along stepwise, controlled, and high-yielding routes via porphyrin → tetrahydroxyisobacteriochlorin metal complexes → isobacteriochlorindilactone metal complexes or porphyrin → tetrahydroxybacteriochlorin → bacteriochlorindilactone (and related) pathways, respectively, are described. A major benefit of these complementary routes over established methods is the simplicity of the isolation of the dilactones because of the reduced number of side products formed. In an alternative approach we report the direct and selective conversion of free base meso-tetrakis(pentafluorophenyl)porphyrin to all isomers of free base isobacteriodilactones using the oxidant cetyltrimethylNMnO. The solid-state structures of some of the isomers and their precursors are reported, providing data on the conformational modulation induced by the derivatizations. We also rationalize computationally their differing thermodynamic stability and electronic properties. In making new efficient routes toward these dilactone isomers available, we enable the further study of this diverse class of porphyrinoids.
卟吩内酯是一种卟啉类化合物，其中母体发色团的一个或多个β,β'-键被内酯部分取代。通过卟啉的直接和非选择性氧化，可以不同程度地获得这些化合物，本文通过卟啉→四羟基异细菌绿素金属配合物→异细菌绿素二内酯金属配合物或卟啉→四羟基细菌绿素→细菌绿素二内酯（和相关）途径，分别以逐步、可控和高产的方式合理合成了所有五种二内酯异构体。与已建立的方法相比，这些互补途径的一个主要优点是由于形成的副产物数量减少，二内酯的分离变得简单。在另一种方法中，我们报告了使用氧化剂十六烷基三甲基 NMnO 直接和选择性地将游离碱基meso-四(五氟苯基)卟啉转化为所有游离碱基异细菌二内酯异构体。报告了一些异构体及其前体的固态结构，提供了关于衍生化诱导的构象调制的数据。我们还通过计算合理推断了它们不同的热力学稳定性和电子性质。通过提供这些二内酯异构体的新的有效途径，我们能够进一步研究这一多样化的卟啉类化合物。
