American Chemical Society
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Nucleophilic Ring Opening of meso-Substituted 5‑Oxaporphyrin by Oxygen, Nitrogen, Sulfur, and Carbon Nucleophiles

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journal contribution
posted on 2014-03-21, 00:00 authored by Kazuhisa Kakeya, Masakatsu Aozasa, Tadashi Mizutani, Yutaka Hitomi, Masahito Kodera
Nucleophilic ring opening of 23H-[21,23-didehydro-10,15,20-tris­(4-methoxycarbonylphenyl)-5-oxaporphyrinato]­(trifluoroacetato)­zinc­(II) with various nucleophiles such as alkoxide, amine, thiolate, and enolate gave 19-substituted bilinone zinc complexes, and they were isolated as free base bilinones. An X-ray crystallographic study demonstrated that the product of 5-oxaporphyrin with sodium methoxide was 21H,23H-(4Z,9Z,15Z)-1,21-dihydro-19-methoxy-5,10,15-tris­(4-methoxycarbonylphenyl)­bilin-1-one with a helicoidal conformation. The structure of the product of 5-oxaporphyrin with an enolate of ethyl acetoacetate was 21H,22H,24H-(4Z,9Z,15Z,19E)-19-(1-ethoxycarbonyl-2-oxopropylidene)-5,10,15-tris­(4-methoxycarbonylphenyl)-1,19,21,24-tetrahydrobilin-1-one, with three inner NH groups. The product with SH was also the same tautomer, 21H,22H,24H-19-thioxo-bilin-1-one, with three NH groups, while the products with RO, RNH2, and RS nucleophiles were 21H,23H-bilin-1-ones with two inner NH groups. The first-order rate constants of the ring opening reaction of 5-oxaporphyrin with 1 M BnOH and BnSH in toluene at 303 K were 3.0 × 10–4 and 6.1 × 10–4 s–1, respectively. The ratio of the rate of alcohol to thiol was much higher than that with methyl iodide, suggesting that 5-oxaporphyrin reacted as a hard electrophile in comparison to methyl iodide. UV–visible spectra of 19-substituted bilinones in CHCl3 at 298 K showed that the absorption maximum of the lower energy band was red-shifted in increasing order of O-substituted (645 nm), S-substituted (668 nm), N-substituted (699 nm), and C-substituted bilinones (706 nm).