3-Cyclobutenyl-1,2-dione-substituted porphyrins. 2. A simple and general entry to quinone-porphyrin-porphyrin-quinone tetrads and related molecules.
3-Cyclobutenyl-1,2-dione-substituted porphyrins. 2. A simple and general entry to quinone-porphyrin-porphyrin-quinone tetrads and related molecules.
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3-环丁烯基-1,2-二酮取代的卟啉。
DOI：
10.1021/jo991382y
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发表时间：
2000
期刊：
影响因子：
--
通讯作者：
Liebeskind,LS
中科院分区：
文献类型：
--
作者：
Shi,X;Liebeskind,LS
通过将锌化的5-取代-10，20-二苯基卟啉（其中取代基为3-环丁烯基-1，2-二酮、各种醌基衍生物和对茴香基）与2，3-二氯-5，6-二氰基醌（DDQ）的CH 2Cl 2溶液简单处理，完成了meso-连接的醌-卟啉-卟啉-醌四联体的合成。以5-（3-环丁烯基-1，2-二酮）-10，20-二苯基卟啉（Zn）为原料合成了锌基卟啉醌。5-（3-环丁烯基-1，2-二酮）-10，20-二苯基卟啉（Zn）的内消旋二聚体也被证明是一种有用的内消旋醌-卟啉-卟啉-醌四联体的前体。这种DDQ为基础的氧化二聚反应似乎是普遍和有效的各种锌5-取代-10，20-二苯基卟啉轴承吸电子和供电子取代基。氧化二聚反应对反应溶剂非常敏感（二聚反应发生在CH 2Cl 2中，而不是在THF中），并且需要锌化卟啉（相应的游离碱卟啉不经历二聚反应）。将这种溶剂效应应用于I2/AgO 2CCF 3与锌卟啉的反应中，只需分别选择二氯甲烷或四氢呋喃作为反应溶剂，即可选择性地制备二聚卟啉或碘卟啉。
The synthesis ofmeso-linked quinone−porphyrin−porphyrin−quinone tetrads has been accomplished by the simple treatment of a CH2Cl2solution of zincated 5-substituted-10,20-diphenylporphyrins (where the substituent = 3-cyclobutenyl-1,2-dione, various quinonyl derivatives, andp-anisyl) with 2,3-dichloro-5,6-dicyanoquinone (DDQ). The zincated porphyrinic quinones were synthesized from 5-(3-cyclobutenyl-1,2-dione)-10,20-diphenylporphyrin(Zn). Themeso-linked dimer of 5-(3-cyclobutenyl-1,2-dione)-10,20-diphenylporphyrin(Zn) was also shown to be a useful precursor tomeso-linked quinone−porphyrin−porphyrin−quinone tetrads. This DDQ-based oxidative dimerization appears to be general and effective for various zincated 5-substituted-10,20-diphenylporphyrins bearing both electron-withdrawing and -donating substituents. The oxidative dimerization was very sensitive to the reaction solvent (dimerization occurred in CH2Cl2, not in THF) and required the zincated porphyrins (the corresponding free base porphyrins did not undergo dimerization). When this solvent effect was applied to the reaction of I2/AgO2CCF3with zincated porphyrins, either the dimeric porphyrins or iodoporphyrins could be selectively prepared simply by selecting methylene chloride or THF as the reaction solvent, respectively.