Von Chlorophyll abstammende gelbe Phyllobiline höherer Pflanzen als umgebungsgesteuerte, chirale Photoschalter

Li, Chengjie; Wurst, Klaus; Jockusch, Steffen; Gruber, Karl; Podewitz, Maren; Liedl, Klaus R.; Kräutler, Bernhard

doi:10.1002/ange.201609481

Cited by 4 publications

(15 citation statements)

References 48 publications

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“…The mean deviation for the more extended planes of ring C/D/A' is 0.061 for pyYCC-Me (Z4-Me), whereas that for the plane of ring C'/D'/A in YCC-Me is 0.040 .T he intermolecular distances for C15-C16' and C15'-C16 of Z4-Me are 3.97 ,t hat is, approximately 0.3 longer than that in YCC-Me. [31] Likewise, the distance betweent he two parallel planes is 3.55 in Z4-Me,t hat is, also slightly longer than in YCC-Me,w here it amounts to 3.47 . [31] Hence,i ntermodular packing in (YCC-Me) 2 ,t he dimero ft he more highly substituted YCC-Me,i sr emarkably more tight than in the dimer (Z4-Me) 2 of the pyro-YCC analogue Z4-Me.…”

Section: Resultsmentioning

confidence: 88%

“…[31] Likewise, the distance betweent he two parallel planes is 3.55 in Z4-Me,t hat is, also slightly longer than in YCC-Me,w here it amounts to 3.47 . [31] Hence,i ntermodular packing in (YCC-Me) 2 ,t he dimero ft he more highly substituted YCC-Me,i sr emarkably more tight than in the dimer (Z4-Me) 2 of the pyro-YCC analogue Z4-Me.…”

Section: Resultsmentioning

confidence: 88%

“…The absolute configuration at C10 of pyYCC-Me Z4-Me was assigned on the basis of the CD spectra of Z4-Me and YCC-Me, the absolute structure of which has been deduced by crystallography. [31] In the crystal,t wo molecules of pyYCC-Me (Z4-Me)f orm a hydrogen-bonded and p-stacked homodimer in a" doubledecker"a rrangement, separated by the ring B/E-section as a spacer,a sr ecently found for YCC-Me (see Figure 5). [31] In these C2-symmetric dimers, the short (C15 = C16) bonds of two Z4-Me molecules are positioned nearly on top of each other.T he ("bilirubin"-type) ring C/D moiety of Z4-Me is nearly planar, with am eand eviation of 0.056 ,s imilar to the situation in YCC-Me (0.041 ).…”

Section: Resultsmentioning

confidence: 89%

“…[31] In the crystal,t wo molecules of pyYCC-Me (Z4-Me)f orm a hydrogen-bonded and p-stacked homodimer in a" doubledecker"a rrangement, separated by the ring B/E-section as a spacer,a sr ecently found for YCC-Me (see Figure 5). [31] In these C2-symmetric dimers, the short (C15 = C16) bonds of two Z4-Me molecules are positioned nearly on top of each other.T he ("bilirubin"-type) ring C/D moiety of Z4-Me is nearly planar, with am eand eviation of 0.056 ,s imilar to the situation in YCC-Me (0.041 ). [31] Likewise, the dihedrala ngles between the nearly coplanarr ings Ca nd Do fZ4-Me (9.18)a nd of YCC-Me (6.28)w ere similarly small.…”

Section: Resultsmentioning

confidence: 89%

“…[31] In these C2-symmetric dimers, the short (C15 = C16) bonds of two Z4-Me molecules are positioned nearly on top of each other.T he ("bilirubin"-type) ring C/D moiety of Z4-Me is nearly planar, with am eand eviation of 0.056 ,s imilar to the situation in YCC-Me (0.041 ). [31] Likewise, the dihedrala ngles between the nearly coplanarr ings Ca nd Do fZ4-Me (9.18)a nd of YCC-Me (6.28)w ere similarly small. The dihedrala ngle between rings E Scheme5.Preparation of pyYCC-Me (Z4-Me)bye sterificationo fpyYCC 4 (BOP = (benzotriazol-1yl-oxy)tris(dimethylamino)phosphonium-hexafluorophosphate, TEA = triethylamine).…”

Section: Resultsmentioning

confidence: 99%

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Pyro‐Phyllobilins: Elusive Chlorophyll Catabolites Lacking a Critical Carboxylate Function of the Natural Chlorophylls

Wurst

Berghold

et al. 2018

Chemistry A European J

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A β‐keto ester grouping is a characteristic of ring E of the chlorophylls (Chls). Its presence has also reinforced the original identification of nonfluorescent Chl catabolites (NCCs) as colorless, amphiphilic phyllobilins (PBs). Polar NCCs were also detected in higher plants, in which a free carboxyl group replaced the ring E ester group. Such NCCs are surprisingly resistant to loss of this carboxyl unit, and NCCs lacking the latter, that is, pyro‐NCCs (pyNCCs), have not been reported. Intrigued by the question of the natural occurrence of pyro‐phyllobilins (pyPBs), we have prepared a representative pyNCC by decarboxylation of a natural NCC. We also converted the pyNCC into its yellow oxidation product, a pyro‐YCC (pyYCC). The solution structures of pyNCC and of pyYCC, and a crystal structure of the pyYCC methyl ester (pyYCC‐Me) were obtained. pyYCC‐Me features the same remarkable H‐bonded and π‐stacked dimer structure as the corresponding natural yellow Chl catabolite (YCC) with the ring E methyl ester group. Indeed, the latter substituent has little effect on the structure, as well as on the unique self‐assembly and photoswitch behavior of yellow PBs.

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Section: Resultsmentioning

confidence: 88%

Section: Resultsmentioning

confidence: 88%

Section: Resultsmentioning

confidence: 89%

Section: Resultsmentioning

confidence: 89%

Section: Resultsmentioning

confidence: 99%

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Pyro‐Phyllobilins: Elusive Chlorophyll Catabolites Lacking a Critical Carboxylate Function of the Natural Chlorophylls

Wurst

Berghold

et al. 2018

Chemistry A European J

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Yellow Dioxobilin‐Type Tetrapyrroles from Chlorophyll Breakdown in Higher Plants—A New Class of Colored Phyllobilins

Erhart

Liu

et al. 2019

Chemistry A European J

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In senescent leaves chlorophyll (Chl) catabolites typically accumulate as colorless tetrapyrroles, classified as formyloxobilin‐type (or type‐I) or dioxobilin‐type (type‐II) phyllobilins (PBs). Yellow type‐I Chl catabolites (YCCs) also occur in some senescent leaves, in which they are generated by oxidation of colorless type‐I PBs. A yellow type‐II PB was recently proposed to occur in extracts of fall leaves of grapevine ( Vitis vinifera ), tentatively identified by its mass and UV/Vis absorption characteristics. Here, the first synthesis of a yellow type‐II Chl catabolite (DYCC) from its presumed natural colorless type‐II precursor is reported. A homogenate of a Spatiphyllum wallisii leaf was used as “green” means of effective and selective oxidation. The synthetic DYCC was fully characterized and identified with the yellow grapevine leaf pigment. As related yellow type‐I PBs do, the DYCC functions as a reversible photoswitch by undergoing selective photo‐induced Z / E isomerization of its C15=C16 bond.

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A Blue Zinc Complex of a Dioxobilin‐Type Pink Chlorophyll Catabolite Exhibiting Bright Chelation‐Enhanced Red Fluorescence

Podewitz

Kräutler

2021

Eur J Inorg Chem

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In senescent fall leaves and in ripening fruit, colorless phyllobilins (PBs) accumulate from breakdown of chlorophyll, from which yellow PBs (phylloxanthobilins) and pink colored PBs (phylloroseobilins) arise in some leaves. The first described PBs were formyloxobilin-type PBs, but dioxobilin-type PBs also occur naturally. Here we report the synthesis and characterization of the blue Zn(II) complex of a dioxobilin-type pink PB, which chelates a Zn(II) ion fast and tightly in an effectively tridentate manner. The optically active Zn complex featured bright chelation enhanced red fluorescence and exhibited strikingly differing spectral properties in methanol and in acetonitrile. Computational studies based on DFT-calculations gave detailed insights into low energy structures of the Zn complex in both solvents and provided support for the proposed role of solvent in the coordination sphere of the bound Zn(II) ion.

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Von Chlorophyll abstammende gelbe Phyllobiline höherer Pflanzen als umgebungsgesteuerte, chirale Photoschalter

Cited by 4 publications

References 48 publications

Pyro‐Phyllobilins: Elusive Chlorophyll Catabolites Lacking a Critical Carboxylate Function of the Natural Chlorophylls

Pyro‐Phyllobilins: Elusive Chlorophyll Catabolites Lacking a Critical Carboxylate Function of the Natural Chlorophylls

Yellow Dioxobilin‐Type Tetrapyrroles from Chlorophyll Breakdown in Higher Plants—A New Class of Colored Phyllobilins

A Blue Zinc Complex of a Dioxobilin‐Type Pink Chlorophyll Catabolite Exhibiting Bright Chelation‐Enhanced Red Fluorescence

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