Suzuki cross-coupling of meso-dibromoporphyrins for the synthesis of functionalized A2B2 porphyrins

Columnar Discotic Mesophases from Novel Non-symmetrically Substituted (Octylsulfanyl) Porphyrazines

“…After removal of the solvent under reduced pressure, the crude product was purified by column chromatography on silica gel using a CH 2 Cl 2 À n-hexane mixture as eluent. 7,8,12,13,17,10,15,. According to the conditions of the General Procedure the reaction of 'free-base' 3a with phenylboronic acid resulted in the isolation of 4a after purification by chromatography on silica gel with a CH 2 Cl 2 Àn-hexane (4:6) mixture as eluent (third band).…”

Oxygen Activation Chemistry of Pacman and Hangman Porphyrin Architectures Based on Xanthene and Dibenzofuran Spacers

“…Given that the etioporphyrin-type substitution patterns of the parent DPX and DPD systems are generally unstable to oxidizing conditions, owing to the unprotected meso positions on the porphyrin rings, it was reasoned that the construction of meso-substituted bisporphyrin Pacman derivatives might display higher catalase (and more generally, oxidative) efficiencies. Scheme 3 presents a modular and general synthetic route for the facile preparation of mesotetraaryl cofacial bisporphyrins affixed to xanthene (DTMPX ¼ ditrimesitylporitylporphyrin xanthene) or dibenzofuran (DTMPD ¼ ditrimesitylporphyrin dibenzofuran) scaffolds using Suzuki cross-coupling methods (140)(141)(142)(143)(144)(145)(146)(147)(148)(149)(150)(151)(152)(153)(154). The mesityl (mes) substituents incorporated into the Pacman motif provide steric bulk, as well as oxidative stability for high-valent metal oxo species (155,156).…”

A New Synthetic Approach to Thiophene‐Nickel(II)porphyrin Hybrid Molecules and their Electrochemical and Computational Investigation

“…173 8C). 10-[2-(2,5-Dibromothien-3-yl)vinyl]-5,15-diphenylporphyrinato-nickel(II) (16) To a mixture of 14 (704 mg, 1.29 mmol) and NaH (60% in mineral oil, 183 mg, 4.58mmol) in DME (10 ml) was added 15 (506 mg, 1.29 mmol) at room temperature. The solution was stirred for 18 h at room temperature.…”

“…[9] In the first step, this was subjected to a Suzuki coupling with an excess of boronic acid 2 [10] (3 equiv. per bromine atom) using a similar procedure to that developed by Vaz et al [16] The reagents were heated in the presence of Pd(Ph 3 ) 4 (13 mol-% relative to bromine) to 60 8C in DMF to achieve the two-fold thiophene-porphyrin junction. Product 3 was isolated in 90% yield by precipitation with water, filtration of a dichloromethane solution through silica gel and recrystallisation from dichloromethane/methanol.…”