Synthesis of the 6,7-bis[2-methoxycarbonyl(1,1- dideutero)-ethyl] derivative of protoporphyrin IX dimethyl ester

Shim, Young Key; Pandey, Ravindra K.; Smith, Kevin M.

doi:10.1002/(sici)1099-1409(200003)4:2<185::aid-jpp179>3.0.co;2-i

Cited by 3 publications

(1 citation statement)

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“…Given that (1) the exchange was incomplete and had an obligatory requirement for the presence of the ferric chelate, and (2) metalation of electron-rich bacteriochlorins is challenging [37], we elected to pursue the de novo synthesis of BC-2 beginning with suitable deuteriated precursors. The synthesis of pyrroles bearing deuteriated β-methyl groups is strongly precedented by work in the porphyrin arena, chiefly by Smith and coworkers [38][39][40][41][42][43][44]. A key question in the present work was whether such a deuteriated pyrrole could be converted with isotopic fidelity to the corresponding bacteriochlorin.…”

Section: Chart 1 Natural Bacterial Photosynthetic Pigmentsmentioning

confidence: 91%

De Novo Synthesis of Bacteriochlorins Bearing Four Trideuteriomethyl Groups

et al. 2022

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Site-specific introduction of isotopes in tetrapyrrole macrocycles provides the foundation for probing physicochemical features germane to photosynthetic energy-transduction processes, but has chiefly been done with porphyrins rather than the more biologically relevant hydroporphyrin analogues of native photosynthetic pigments. A prior study incorporated pairwise 13C or 15N atoms in the skeleton of a bacteriochlorin containing a gem-dimethyl group in each pyrroline ring. Here, a complementary effort is reported that installs deuterium atoms in substituents at the perimeter of a bacteriochlorin. Thus, perdeuteriated 3-methyl-2,4-pentanedione was converted in an 8-step synthesis via the intermediacy of tert-butyl 5-formyl-3,4-bis(trideuteriomethyl)pyrrole-2-carboxylate to the 2,3,12,13-tetrakis(trideuteriomethyl)-8,8,18,18-tetramethylbacteriochlorin (BC-2). The fidelity of isotope substitution was maintained throughout the synthesis. Resonance Raman spectroscopy of the copper chelate (CuBC-2) revealed that addition of the four β-pyrrolic substituents alone is not sufficient to account for the vibronic complexity observed for the copper chelate of bacteriochlorophyll a (CuBChl a). The increased vibronic activity exhibited by the natural pigments and CuBChl a must arise from the increased structural complexity of the macrocycle.

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Section: Chart 1 Natural Bacterial Photosynthetic Pigmentsmentioning

confidence: 91%

De Novo Synthesis of Bacteriochlorins Bearing Four Trideuteriomethyl Groups

et al. 2022

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The Red Color of Life Transformed – Synthetic Advances and Emerging Applications of Protoporphyrin IX in Chemical Biology

Sitte

Senge

2020

Eur J Org Chem

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Protoporphyrin IX (PPIX) is the porphyrin scaffold of heme b, a ubiquitous prosthetic group of proteins responsible for oxygen binding (hemoglobin, myoglobin), electron transfer (cytochrome c) and catalysis (cytochrome P450, catalases, peroxidases). PPIX and its metallated derivatives frequently find application as therapeutic agents, imaging tools, catalysts, sensors and in light harvesting. The vast toolkit of accessible porphyrin functionalization reactions enables easy synthetic modification of PPIX to meet the requirements for its multiple uses. In the past few years, particular interest has arisen in exploiting the interaction of PPIX and its synthetic derivatives with biomolecules such as DNA and heme‐binding proteins to evolve molecular devices with new functions as well as to uncover potential therapeutic toeholds. This review strives to shine a light on the most recent developments in the synthetic chemistry of PPIX and its uses in selected fields of chemical biology.

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