Modification of the Peripheral Substituents in Chlorophylls a and b and Their Derivatives

Pavlov, V. Yu.; Ponomarev, G. V.

doi:10.1002/chin.200448240

Cited by 7 publications

(15 citation statements)

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“…164 An alternative method for hydrogenation entails a multistep sequence of reactions, which at first glance might seem unnecessary but on reflection has considerable attractions. Thus, nitration of H 2 TPP afforded the mononitro derivative 4-H 2 16. The presence of the nitro group activates the adjacent carbon toward attack by borohydride, whereupon the βnitrochlorin 4-H 2 17 was formed.…”

Section: Alternative Methods For Hydrogenationmentioning

confidence: 99%

Synthetic Chlorins, Possible Surrogates for Chlorophylls, Prepared by Derivatization of Porphyrins

2016

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Chlorophylls make Earth green, are the central constituents in the engine of photosynthesis, and not surprisingly have garnered immense attention. A chlorin, the core chromophore of a chlorophyll, is a dihydroporphyrin macrocycle that contains one pyrroline ring and three pyrrole rings. The dominant method for the synthesis of chlorins has entailed the derivatization of porphyrins. The present review covers the ostensibly simple conversion of porphyrins, regardless of synthetic or biological origin, to chlorins. The period covered encompasses the entire history since the beginnings of chlorin synthetic chemistry in the early 20th century through 2015. Representative transformations include hydrogenation, cycloaddition, annulation, and diverse "breaking and mending" approaches. Altogether, the synthesis of >1000 chlorins or chlorin-like compounds (containing >50 distinct pyrroline motifs) is described. Such diversity animates the question "what structural features are essential for a chlorin to resemble chlorophyll?" To begin to address the structure-spectrum relationship, > 250 absorption spectra are provided for representative structures. The synthesis and spectral properties of the vast collection of compounds described herein are expected to illuminate the scope to which synthetic chlorins can serve as surrogates for chlorophylls and be exploited in diverse ways.

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Section: Alternative Methods For Hydrogenationmentioning

confidence: 99%

Synthetic Chlorins, Possible Surrogates for Chlorophylls, Prepared by Derivatization of Porphyrins

2016

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“…For in depth reviews on chlorophyll chemistry see the book by Scheer and articles therein [11]. The newer literature is accessible through works by Pavlov and Ponomarev [79], Nyman and Hynninen [68], Pandey [80,81], Mironov [82] and the excellent contributions from Tamiaki's group [83].…”

Section: Fundamental Aspects Of Chlorophyll Chemistrymentioning

confidence: 99%

Chlorophylls, Symmetry, Chirality, and Photosynthesis

et al. 2014

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Chlorophylls are a fundamental class of tetrapyrroles and function as the central reaction center, accessory and photoprotective pigments in photosynthesis. Their unique individual photochemical properties are a consequence of the tetrapyrrole macrocycle, the structural chemistry and coordination behavior of the phytochlorin system, and specific substituent pattern. They achieve their full potential in solar energy conversion by working in concert in highly complex, supramolecular structures such as the reaction centers and light-harvesting complexes of photobiology. The biochemical function of these structures depends on the controlled interplay of structural and functional principles of the apoprotein and pigment cofactors. Chlorophylls and bacteriochlorophylls are optically active molecules with several chiral centers, which are necessary for their natural biological function and the assembly of their supramolecular complexes. However, in many cases the exact role of chromophore stereochemistry in the biological context is unknown. This review gives an overview of chlorophyll research in terms of basic function, biosynthesis and their functional and structural role in photosynthesis. It highlights aspects of chirality and symmetry of chlorophylls to elicit further interest in their role in nature.

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“…16,21,24- 29 The procedures gave a variety of esters in a high yield but additional preparation of carboxylic acids from the original propionates was required. 30 Acidic transesterification was widely applicable for synthesis of esters and successfully gave some compounds possessing 17 2 -COOR simply by stirring a mixture of the original ester and ROH in the presence of an acid. 16, 31 During the acidic treatment, the central magnesium was removed easily (pheophytinization) 32 and metal-free products were afforded.…”

Section: Synthesis Of Zinc Bacteriochlorophyll-d Analogues With Vario...mentioning

confidence: 99%

Synthesis of zinc bacteriochlorophyll-d analogues with various 17-substituents and their chlorosomal self-aggregates in non-polar organic solvents

Tamiaki

Michitsuji

Shibata

2008

Photochem Photobiol Sci

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Zinc 3(1)-demethyl-bacteriopheophorbides-d possessing various 17-propionate residue (17(2)-COOCH2-) were prepared as models of light-harvesting pigments in major photosynthetic antennae of green bacteria. The synthetic compounds were monomeric in polar organic solvents to give the same visible absorption spectra, but self-aggregated in non-polar organic solvents to afford large oligomers with broadened and red-shifted absorption bands. The peak positions were identical for all the self-aggregates but the widths of the redmost (Qy) bands were dependent upon the substituents. More hydrophobic and less sterically hindered hydrocarbon moieties as the esterifying group sharpened oligomeric Qy bands, giving less inhomogeneous supramolecular structures due to stabilization of the self-aggregates. In the reverse esters (17(2)-CH2OCO-) structurally isomeric to the above compounds, the same optical behavior was observed. Movement of the oxo group from the 17(3)- to 17(5)-position (17(2)-COOCH2--->17(2)-CH2OCO-) slightly increased the widths of self-aggregated Qy bands without change of the peak positions, where minor less self-aggregated components would enhance in the solution due to a little more stabilization of such species by the 17(4)-carbonyl group.

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Modification of the Peripheral Substituents in Chlorophylls a and b and Their Derivatives

Abstract: For Abstract see ChemInform Abstract in Full Text.

Cited by 7 publications

References 1 publication

Synthetic Chlorins, Possible Surrogates for Chlorophylls, Prepared by Derivatization of Porphyrins

Synthetic Chlorins, Possible Surrogates for Chlorophylls, Prepared by Derivatization of Porphyrins

Chlorophylls, Symmetry, Chirality, and Photosynthesis

Synthesis of zinc bacteriochlorophyll-d analogues with various 17-substituents and their chlorosomal self-aggregates in non-polar organic solvents

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