title: 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.
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.
authors.affiliation: College of Chemistry and Chemical Engineering, Hunan University, Changsha 410082, China.
authors.forename: Li-Mei
authors.initials: LM
authors.lastname: Jin
authors.forename: Liang
authors.initials: L
authors.lastname: Chen
authors.forename: Juan-Juan
authors.initials: JJ
authors.lastname: Yin
authors.forename: Jin-Ming
authors.initials: JM
authors.lastname: Zhou
authors.forename: Can-Cheng
authors.initials: CC
authors.lastname: Guo
authors.forename: Qing-Yun
authors.initials: QY
authors.lastname: Chen