Rational Synthesis of meso- or β- Fluoroalkylporphyrin Derivatives via Halo-fluoroalkylporphyrin Precursors:  Electronic and Steric Effects on Regioselective Electrophilic Substitution in 5-Fluoroalkyl-10,20-diarylporphyrins

• Published in: Journal of organic chemistry 2006-01, Vol.71 (2), p.527-536
• Main Authors: JIN, Li-Mei, CHEN, Liang, YIN, Juan-Juan, ZHOU, Jin-Ming, GUO, Can-Cheng, CHEN, Qing-Yun
• Format: Article
• Language: English
• Subjects: Alicyclic compounds, terpenoids, prostaglandins, steroids; Chemistry; Exact sciences and technology; Organic chemistry; Preparations and properties; Prostaglandins
• ISSN: 0022-3263; 1520-6904
• DOI: 10.1021/jo051672g

[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.