Synthesis of covalently linked dimeric derivatives of chlorophyll a, pyrochlorophyll a, chlorophyll b, and bacteriochlorophyll a

Michael R Wasielewski, Walter A. Svec

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Abstract

Bis(chlorophyllide) ethylene glycol diesters were prepared for each of the title compounds. Pheophytins a and b isolated from alfalfa and bacteriochlorophyll a isolated from R. sphaeroides were treated with 80% aqueous trifluoroacetic acid to yield the corresponding pheophorbides. Pyropheophorbide was prepared by a literature procedure. Carbonic anhydride and benzotriazole-1-methanesulfonate activation methods were used in the esterification of the pheophorbides with ethylene glycol at ambient temperature. Each method yielded 75% + of the pheophorbide ethylene glycol monoester. These monoesters were treated with equimolar amounts of the corresponding pheophorbide by using benzotriazole-1-methanesulfonate/4-(dimethylamino)pyridine in CH2Cl2 or dicyclohexylcarbodiimide/4-(dimethylamino)pyridine in CH2Cl2 at ambient temperature. Yields of bis(pheophorbide) ethylene glycol diesters averaged about 50% for the former method and 70% for the latter method. Insertion of the magnesium atoms into the a series macrocycles was accomplished with iodomagnesium 2,6-di-tert-butyl-4-methylphenolate, IMgBHT, in CH2Cl2, while the metalation of the 6 and bacterial series macrocycles was carried out with a mixture of IMgBHT and lithium 2,2,6,6-tetramethylpiperidide in thiophene, all at ambient temperature. Both mono- and dimetalated derivatives were isolated and characterized in each case.

Original languageEnglish
Pages (from-to)1969-1974
Number of pages6
JournalJournal of Organic Chemistry
Volume45
Issue number10
Publication statusPublished - 1980

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Bacteriochlorophylls
Ethylene Glycol
Derivatives
Chlorophyllides
Dicyclohexylcarbodiimide
Trifluoroacetic Acid
Thiophenes
Esterification
Carbon Dioxide
Temperature
Magnesium
Chemical activation
Atoms
chlorophyll a
chlorophyll b
methanesulfonic acid
benzotriazole
pyridine

ASJC Scopus subject areas

  • Organic Chemistry

Cite this

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title = "Synthesis of covalently linked dimeric derivatives of chlorophyll a, pyrochlorophyll a, chlorophyll b, and bacteriochlorophyll a",
abstract = "Bis(chlorophyllide) ethylene glycol diesters were prepared for each of the title compounds. Pheophytins a and b isolated from alfalfa and bacteriochlorophyll a isolated from R. sphaeroides were treated with 80{\%} aqueous trifluoroacetic acid to yield the corresponding pheophorbides. Pyropheophorbide was prepared by a literature procedure. Carbonic anhydride and benzotriazole-1-methanesulfonate activation methods were used in the esterification of the pheophorbides with ethylene glycol at ambient temperature. Each method yielded 75{\%} + of the pheophorbide ethylene glycol monoester. These monoesters were treated with equimolar amounts of the corresponding pheophorbide by using benzotriazole-1-methanesulfonate/4-(dimethylamino)pyridine in CH2Cl2 or dicyclohexylcarbodiimide/4-(dimethylamino)pyridine in CH2Cl2 at ambient temperature. Yields of bis(pheophorbide) ethylene glycol diesters averaged about 50{\%} for the former method and 70{\%} for the latter method. Insertion of the magnesium atoms into the a series macrocycles was accomplished with iodomagnesium 2,6-di-tert-butyl-4-methylphenolate, IMgBHT, in CH2Cl2, while the metalation of the 6 and bacterial series macrocycles was carried out with a mixture of IMgBHT and lithium 2,2,6,6-tetramethylpiperidide in thiophene, all at ambient temperature. Both mono- and dimetalated derivatives were isolated and characterized in each case.",
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T1 - Synthesis of covalently linked dimeric derivatives of chlorophyll a, pyrochlorophyll a, chlorophyll b, and bacteriochlorophyll a

AU - Wasielewski, Michael R

AU - Svec, Walter A.

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N2 - Bis(chlorophyllide) ethylene glycol diesters were prepared for each of the title compounds. Pheophytins a and b isolated from alfalfa and bacteriochlorophyll a isolated from R. sphaeroides were treated with 80% aqueous trifluoroacetic acid to yield the corresponding pheophorbides. Pyropheophorbide was prepared by a literature procedure. Carbonic anhydride and benzotriazole-1-methanesulfonate activation methods were used in the esterification of the pheophorbides with ethylene glycol at ambient temperature. Each method yielded 75% + of the pheophorbide ethylene glycol monoester. These monoesters were treated with equimolar amounts of the corresponding pheophorbide by using benzotriazole-1-methanesulfonate/4-(dimethylamino)pyridine in CH2Cl2 or dicyclohexylcarbodiimide/4-(dimethylamino)pyridine in CH2Cl2 at ambient temperature. Yields of bis(pheophorbide) ethylene glycol diesters averaged about 50% for the former method and 70% for the latter method. Insertion of the magnesium atoms into the a series macrocycles was accomplished with iodomagnesium 2,6-di-tert-butyl-4-methylphenolate, IMgBHT, in CH2Cl2, while the metalation of the 6 and bacterial series macrocycles was carried out with a mixture of IMgBHT and lithium 2,2,6,6-tetramethylpiperidide in thiophene, all at ambient temperature. Both mono- and dimetalated derivatives were isolated and characterized in each case.

AB - Bis(chlorophyllide) ethylene glycol diesters were prepared for each of the title compounds. Pheophytins a and b isolated from alfalfa and bacteriochlorophyll a isolated from R. sphaeroides were treated with 80% aqueous trifluoroacetic acid to yield the corresponding pheophorbides. Pyropheophorbide was prepared by a literature procedure. Carbonic anhydride and benzotriazole-1-methanesulfonate activation methods were used in the esterification of the pheophorbides with ethylene glycol at ambient temperature. Each method yielded 75% + of the pheophorbide ethylene glycol monoester. These monoesters were treated with equimolar amounts of the corresponding pheophorbide by using benzotriazole-1-methanesulfonate/4-(dimethylamino)pyridine in CH2Cl2 or dicyclohexylcarbodiimide/4-(dimethylamino)pyridine in CH2Cl2 at ambient temperature. Yields of bis(pheophorbide) ethylene glycol diesters averaged about 50% for the former method and 70% for the latter method. Insertion of the magnesium atoms into the a series macrocycles was accomplished with iodomagnesium 2,6-di-tert-butyl-4-methylphenolate, IMgBHT, in CH2Cl2, while the metalation of the 6 and bacterial series macrocycles was carried out with a mixture of IMgBHT and lithium 2,2,6,6-tetramethylpiperidide in thiophene, all at ambient temperature. Both mono- and dimetalated derivatives were isolated and characterized in each case.

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