Synthesis of [3‐13C]‐, [4‐13C]‐ and [11‐13C]‐porphobilinogen

Dawadi, Prativa B. S.; Schulten, Els; Lugtenburg, J.

doi:10.1002/jlcr.1602

Cited by 3 publications

(3 citation statements)

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“…Both approaches-global enrichment and site-specific incorporation-have been employed to elucidate biosynthetic pathways and for spectroscopic studies. An example of the latter makes use of δ-aminolevulinic acid [19] and porphobilinogen [20] with controlled isotopic incorporation at numerous sites owing to the work of Lugtenburg and coworkers. It warrants mention, however, that eight molecules of δ-aminolevulinic acid combine to form a native macrocycle, hence the presence of a single 13 C or 15 N-atom in δ-aminolevulinic acid typically results in four or eight such atoms in the resulting macrocycle; moreover, the pattern is irregular given the nature of the biosynthetic pathway, as shown in the example [15];…”

Section: Chart 1 Natural Bacterial Photosynthetic Pigmentsmentioning

confidence: 99%

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: 99%

De Novo Synthesis of Bacteriochlorins Bearing Four Trideuteriomethyl Groups

et al. 2022

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“…The Strecker reaction of NH 4 Cl ( 1 ), two equivalents of HCHO ( 2 ) and KCN ( 3 ) afforded the product hexahydro-1,3,5-triazine-1,3,5-tris(acetonitrile) ( 4 ) [46]. Treatment of compound 4 with acid in ethanol yielded 2-aminoacetonitrile ( 5 ) and diethoxymethane.…”

Section: Synthesis Of 22 Amino Acidsmentioning

confidence: 99%

Access to Any Site Directed Stable Isotope (2H, 13C, 15N, 17O and 18O) in Genetically Encoded Amino Acids

Dawadi

Lugtenburg

2013

Molecules

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Proteins and peptides play a preeminent role in the processes of living cells. The only way to study structure-function relationships of a protein at the atomic level without any perturbation is by using non-invasive isotope sensitive techniques with site-directed stable isotope incorporation at a predetermined amino acid residue in the protein chain. The method can be extended to study the protein chain tagged with stable isotope enriched amino acid residues at any position or combinations of positions in the system. In order to access these studies synthetic methods to prepare any possible isotopologue and isotopomer of the 22 genetically encoded amino acids have to be available. In this paper the synthetic schemes and the stable isotope enriched building blocks that are available via commercially available stable isotope enriched starting materials are described.

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“…On the other hand, transformation of a porphyrin that bears a single isotopic atom can result in a mixture of up to four isotopomeric bacteriochlorins. A complementary route toward isotopically substituted bacteriochlorophylls relies on biosynthetic transformations; however, even with the availability of rather advanced precursors (such as δ-aminolevulinic acid or porphobilinogen) that bear site-specific isotopic substitution, , the resulting macrocycles bear isotopic atoms at numerous sites (Scheme ). Such bacteriochlorophylls have numerous valuable applications but are not generally well suited for studies aimed at developing spin-density maps or vibrational force fields because of the spectral complexity arising from multiple isotopic atoms.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of 24 Bacteriochlorin Isotopologues, Each Containing a Symmetrical Pair of¹³C or¹⁵N Atoms in the Inner Core of the Macrocycle

2014

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Synthetic bacteriochlorins containing site-specific isotopic substitution enable spectroscopic interrogation to delineate physicochemical features relevant to bacteriochlorophylls in photosynthesis but have been little explored. A de novo synthesis has been employed to prepare bacteriochlorins wherein each macrocycle contains a pair of (13)C or (15)N atoms yet lacks substituents other than a geminal dimethyl group in each pyrroline ring. Preparation of a dihydrodipyrrin–acetal with single-isotopic substitution gives rise to a bacteriochlorin that contains two isotopic substitutions symmetrically disposed by a 180° rotation about the normal to the plane of the macrocycle. Eight such isotopically substituted bacteriochlorins were prepared from commercially available reactants (bacteriochlorin sites): ((13)C)paraformaldehyde (1, 11); ((13)C)formamide (4, 14); triethyl ((13)C)orthoformate (5, 15); K(13)CN (6, 16); (13)CH3NO2 (9, 19); N,N-dimethyl((13)C)formamide (10, 20); ((15)N)pyrrole (21, 23); CH3(15)NO2 (22, 24). Some loss of (15)N upon TiCl3-mediated McMurry-type ring closure of a nitro((15)N)hexanone is attributed to a parallel sequence of three reactions (Nef, exchange with natural-abundance NH4OAc buffer, and Paal–Knorr ring closure) leading to the dihydrodipyrrin–acetal. Zinc and copper chelates of each bacteriochlorin also were prepared. Together, the 24 bacteriochlorin isotopologues should provide valuable benchmarks for understanding ground- and excited-state molecular physics of the macrocycles related to photosynthetic function of bacteriochlorophylls.

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Synthesis of [3‐¹³C]‐, [4‐¹³C]‐ and [11‐¹³C]‐porphobilinogen

Cited by 3 publications

References 11 publications

De Novo Synthesis of Bacteriochlorins Bearing Four Trideuteriomethyl Groups

De Novo Synthesis of Bacteriochlorins Bearing Four Trideuteriomethyl Groups

Access to Any Site Directed Stable Isotope (2H, 13C, 15N, 17O and 18O) in Genetically Encoded Amino Acids

Synthesis of 24 Bacteriochlorin Isotopologues, Each Containing a Symmetrical Pair of¹³C or¹⁵N Atoms in the Inner Core of the Macrocycle

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Synthesis of [3‐13C]‐, [4‐13C]‐ and [11‐13C]‐porphobilinogen

Cited by 3 publications

References 11 publications

De Novo Synthesis of Bacteriochlorins Bearing Four Trideuteriomethyl Groups

De Novo Synthesis of Bacteriochlorins Bearing Four Trideuteriomethyl Groups

Access to Any Site Directed Stable Isotope (2H, 13C, 15N, 17O and 18O) in Genetically Encoded Amino Acids

Synthesis of 24 Bacteriochlorin Isotopologues, Each Containing a Symmetrical Pair of13C or15N Atoms in the Inner Core of the Macrocycle

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Synthesis of [3‐¹³C]‐, [4‐¹³C]‐ and [11‐¹³C]‐porphobilinogen

Synthesis of 24 Bacteriochlorin Isotopologues, Each Containing a Symmetrical Pair of¹³C or¹⁵N Atoms in the Inner Core of the Macrocycle