Novel 21,23-Ditelluraporphyrins and the First 26,28-Ditellurasapphyrin and 30,33-Ditellurarubyrin

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• 作者：Bharathwaj Sathyamoorthy ; Abram Axelrod ; Victoria Farwell ; Stephanie M. Bennett ; Brandon D. Calitree ; Jason B. Benedict ; Dinesh K. Sukumaran ; Michael R. Detty
• 刊名：Organometallics
• 出版年：2010
• 出版时间：August 9, 2010
• 年：2010
• 卷：29
• 期：15
• 页码：3431-3441
• 全文大小：1139K
• 年卷期：v.29,no.15(August 9, 2010)
• ISSN：1520-6041

文摘

21,23-Ditelluraporphyrins 3, 9, and 16−18 bearing phenyl, 4-methoxyphenyl, and/or 3,4,5-trimethoxyphenyl meso substituents were prepared by the condensation of 2,5-di[hydroxy(aryl)methyl]tellurophenes 12 with 2,5-di[2-pyrrolo(aryl)methyl]tellurophenes 15 in the presence of BF₃−etherate followed by oxidation with p-chloranil. Compounds 15 were prepared from tellurophenes 12 with pyrrole and BF₃−etherate. Tellurophenes 12 were prepared in 44−72% isolated yield by the addition of 1,6-diarylhexa-2,4-diyn-1,6-diols 13 to the reduction product of Te powder and LiBHEt₃. No additional Lewis acid was necessary in these reactions. Coupling of 1-aryl-2-propyn-1-ols (14) with CuCl, pyridine, and air in MeOH gave diyndiols 13. 26,28-Ditellurasapphyrin 10 was isolated in 0.6% yield from the reaction mixture that produced 9 in 12% isolated yield. The X-ray structure of 10 showed a nearly planar sapphyrin core with the Te atoms of both tellurophene rings pointing to the center of the core. 30,33-Ditellurarubyrin 11 was isolated in 32% yield by the reaction of two equivalents of trifluoroacetic acid with tellurophene dipyrrane 15c. ¹²⁵Te NMR spectra were recorded for the compounds of this study.