De Novo Synthesis of Bacteriochlorins Bearing Four Trideuteriomethyl Groups

Jing, Haoyu; Tang, Qun; Bocian, David F.; Lindsey, Jonathan S.

doi:10.3390/org3010002

Title: De Novo Synthesis of Bacteriochlorins Bearing Four Trideuteriomethyl Groups

Journal Article · Mon Feb 07 00:00:00 EST 2022 · Organics

DOI:https://doi.org/10.3390/org3010002· OSTI ID:1843853

; Tang, Qun; Bocian, David F.;

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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Sponsoring Organization:: USDOE

Grant/Contract Number:: FG02-05ER15661

OSTI ID:: 1843853

Journal Information:: Organics, Journal Name: Organics Vol. 3 Journal Issue: 1; ISSN 2673-401X

Publisher:: MDPI AGCopyright Statement

Country of Publication:: Country unknown/Code not available

Language:: English

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