通过卤代氟烷基卟啉前体合理合成内消旋或β-氟烷基卟啉衍生物：5-氟烷基-10,20-二芳基卟啉区域选择性亲电取代的电子和空间效应

Rational synthesis of meso- or beta- fluoroalkylporphyrin derivatives via halo-fluoroalkylporphyrin precursors: electronic and steric effects on regioselective electrophilic substitution in 5-fluoroalkyl-10,20-diarylporphyrins.

作者信息

Jin Li-Mei, Chen Liang, Yin Juan-Juan, Zhou Jin-Ming, Guo Can-Cheng, Chen Qing-Yun

机构信息

College of Chemistry and Chemical Engineering, Hunan University, Changsha 410082, China.

出版信息

J Org Chem. 2006 Jan 20;71(2):527-36. doi: 10.1021/jo051672g.

DOI:10.1021/jo051672g

PMID:16408960

Abstract

[reaction: see text] Electrophilic nitration, formylation or bromination of metalated 5-fluoroalkyl-10,20-diphenylporphyrin (fluoroalkyl = CF3, ClCF2CF2, n-C6F13) proceeded with high regioselectivity, exclusively affording corresponding meso-substituted porphyrins, while the iodination reaction mainly took place at the adjacent beta site giving 2-iodo-10-fluoroalkyl-5,15-diphenylporphyrin. Suzuki, Sonogashira, and trifluoromethylation reactions of the obtained 5-bromo-15-fluoroalkyl-10,20-diphenylporphyrins or 2-iodo-10-fluoroalkyl-5,15-diphenylporphyrins could perform smoothly to give the corresponding various meso- or beta-functionalized fluoroalkylated porphyrin derivatives. Accordingly, two meso-to-meso butadiyne-bridged bisporphyrin dimers and two beta-to-beta butadiyne-linked dimeric porphyrins were prepared by the coupling reactions of 5-ethynyl-15-fluoroalkyl-10,20-diphenylporphyrins and 2-ethynyl-10-fluoroalkyl-5,15-diphenylporphyrins, respectively.

摘要

[反应：见正文] 金属化的5-氟烷基-10,20-二苯基卟啉（氟烷基 = CF3、ClCF2CF2、n-C6F13）的亲电硝化、甲酰化或溴化反应具有高区域选择性，专一性地生成相应的中位取代卟啉，而碘化反应主要发生在相邻的β位，生成2-碘-10-氟烷基-5,15-二苯基卟啉。所得的5-溴-15-氟烷基-10,20-二苯基卟啉或2-碘-10-氟烷基-5,15-二苯基卟啉的铃木反应、 Sonogashira反应和三氟甲基化反应能够顺利进行，得到相应的各种中位或β-官能化的氟烷基化卟啉衍生物。因此，分别通过5-乙炔基-15-氟烷基-10,20-二苯基卟啉和2-乙炔基-10-氟烷基-5,15-二苯基卟啉的偶联反应制备了两种中位到中位的丁二炔桥连双卟啉二聚体和两种β到β的丁二炔连接的二聚卟啉。