Department of Chemistry, University of Connecticut, Unit 3060, Storrs, CT 06269-3060, USA.
Org Biomol Chem. 2010 Apr 21;8(8):1951-65. doi: 10.1039/b924539a.
The refined syntheses, modification, and first X-ray structural characterization of meso-tetraarylporphyrin-derived beta-tetraolbacteriochlorins are described. These investigations assign the relative stereochemistry of their two isomers (both cis-vic-diol pairs on the same or opposite sides of the porphyrin plane), an assignment that could not be provided by NMR, UV-vis or fluorescence spectroscopy, or mass spectrometry. Moreover, the first crystal structures of a 2-hydroxychlorin and a 2,3-dihydroxychlorin, as its dimethylether, are reported. Dihydroxylation and diimide reduction of the dimethoxychlorin result in the formation of stable mixed-functionality bacteriochlorins. The photophysical properties (UV-vis absorption and fluorescence emission) of all chromophores are contrasted against each other, delineating the electronic effects of diol substitution and conformational modulation. Lastly, the acid-induced dehydration/demethoxylation of the tetraol-, dioldimethoxy-, and tetramethoxybacteriochlorins to provide chlorins is delineated.
中四芳基卟啉衍生的β-四醇杆菌绿素的精细合成、修饰及首次 X 射线结构表征。这些研究确定了它们两个异构体（卟啉平面同侧或异侧的顺式- Vic-二醇对）的相对立体化学，这一分配无法通过 NMR、UV-vis 或荧光光谱学或质谱法提供。此外，还报道了 2-羟基氯素及其二甲醚的 2,3-二羟基氯素的首个晶体结构。二氧杂氯素的二羟基化和二酰亚胺还原导致稳定的多功能杆菌绿素的形成。所有生色团的光物理性质（UV-vis 吸收和荧光发射）相互对比，描绘了二醇取代和构象调制的电子效应。最后，阐述了四醇、二氧代二甲氧基和四甲氧基杆菌绿素在酸诱导下脱水/去甲氧基化为叶绿素的过程。
