Rotational deviation of 3-acetyl group from cyclic tetrapyrrole π-plane in synthetic bacteriochlorophyll-a analogs by 20-substitution

Tamiaki, Hitoshi; Kotegawa, Yuki; Mizutani, Kana

doi:10.1016/j.bmcl.2008.10.031

Cited by 25 publications

(5 citation statements)

References 14 publications

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“…Similar steric effects in the other C3-substituted Chl derivatives were available in previous reports. , Inductive effect of the C3 substituent could not be ruled out.…”

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confidence: 63%

Synthesis, Structure, and Optical and Redox Properties of Chlorophyll Derivatives Directly Coordinating Ruthenium Bisbipyridine at the Peripheral β-Diketonate Moiety

2013

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The diketonate group of the peripheral position in chlorophyll derivatives 1 and 2 coordinated ruthenium bisbipyridine to give direct linkages 3-5 of the chlorin ring with the Ru(II) complex. Zinc metalation of the central position in the chlorin ring of free base 3 afforded the Ru-Zn binuclear complex 3-Zn. Because the diketonate group at the C3 position of chlorophyll derivatives coordinated to bulky Ru(bpy)2(2+), the plane of the diketonate group was twisted from the chlorin π ring in synthetic 3-5 and 3-Zn to lead to a partial deconjugation and a slight blue shift of the longest wavelength electronic absorption band in dichloromethane. A broad metal-to-ligand charge-transfer absorption band derived from the Ru complex was observed around 500 nm, in addition to visible absorption bands from the chlorophyll moiety. Chlorophyll derivatives 3-5 and 3-Zn directly coordinating the ruthenium complex were less fluorescent in dichloromethane than chlorophyll-diketonate ligands 1, 2, and 1-Zn due to the heavy atom effect of the ruthenium in a molecule. The coordination to the ruthenium complex moiety at the peripheral position shifted the electrochemical reduction of the chlorin part in acetonitrile to a negative potential, and the coordination to zinc at the central position decreased the redox potentials. Chemical modification of the bipyridine and diketonate ligands of the ruthenium complexes greatly affected the redox potentials of Ru(II)/(III) and/or Ru(II)/(I) but minimally the redox properties of the chlorin moiety. Substitution with electron-donating groups shifted the former to a negative potential but only barely shifted the latter. The zinc metalation caused no apparent shifts for the redox potentials of the Ru center.

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“…Similar steric effects in the other C3-substituted Chl derivatives were available in previous reports. , Inductive effect of the C3 substituent could not be ruled out.…”

supporting

confidence: 63%

Synthesis, Structure, and Optical and Redox Properties of Chlorophyll Derivatives Directly Coordinating Ruthenium Bisbipyridine at the Peripheral β-Diketonate Moiety

2013

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“…1) rotated the 3-acetyl group toward the perpendicular direction of the chlorin p-plane, due to the remote steric interaction through the 2-methyl group. 5 Here we report the systematic synthesis of 3-acyl-chlorins 1 by oxidation of secondary alcohols 2 prepared by addition of R to the 3-formyl group of methyl pyropheophorbide-d 1a (R¼H) and their visible absorption spectra in dichloromethane. The 3 1 -substituents (R) of 1 affected the visible spectra including their Qy maxima due to the steric interaction between the 3-acyl and its neighboring Scheme 1.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of methyl pyropheophorbide-d derivatives possessing the 3-acyl groups and their electronic absorption spectra

et al. 2016

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“…Dipyrromethanes are widely being used as important precursors for porphyrin syntheses,, in particular, for the synthesis of asymmetric polypyrrolic compounds, and also being used in the field of materials science, medicine and optics . Now a days, its applications have been well demonstrated to synthesize gold nanoparticles .…”

Section: Introductionmentioning

confidence: 99%

Imidazolium Zwitterionic Molten Salt: An Efficient Organocatalyst under Neat Conditions at Room Temperature for the Synthesis of Dipyrromethanes as well as Bis(indolyl)methanes

et al. 2018

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An imidazole-based zwitterionic-salt, 4-(3-methylimidazolium) butane sulfonate (MBS), has been found to be an efficient organocatalyst for the synthesis of dipyrromethanes as well as bis(indolyl)methanes at room temperature under solvent-free conditions (neat) in high yields. The reaction procedure is very simple and a large variety of aldehydes have been examined under similar conditions for indoles and pyrroles. The catalytic reaction proceeded very smoothly and showed high chemoselectivity. Clean reaction, ease of product isolation/purification, easily accessible reactants, metal and solvent-free and environmentally friendly reaction conditions are the notable advantages of the present methodology.

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Rotational deviation of 3-acetyl group from cyclic tetrapyrrole π-plane in synthetic bacteriochlorophyll-a analogs by 20-substitution

Cited by 25 publications

References 14 publications

Synthesis, Structure, and Optical and Redox Properties of Chlorophyll Derivatives Directly Coordinating Ruthenium Bisbipyridine at the Peripheral β-Diketonate Moiety

Synthesis, Structure, and Optical and Redox Properties of Chlorophyll Derivatives Directly Coordinating Ruthenium Bisbipyridine at the Peripheral β-Diketonate Moiety

Synthesis of methyl pyropheophorbide-d derivatives possessing the 3-acyl groups and their electronic absorption spectra

Imidazolium Zwitterionic Molten Salt: An Efficient Organocatalyst under Neat Conditions at Room Temperature for the Synthesis of Dipyrromethanes as well as Bis(indolyl)methanes

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