title: Alternative synthesis of 3-acetyl, 3-epoxy, and 3-formyl chlorins from a 3-vinyl chlorin, methyl pyropheophorbide-a, via iodination.
abstract: We developed novel methods to convert the C3-vinyl group of a chlorophyll derivative, methyl pyropheophorbide-a, into an acetyl group, an epoxy group, and a formyl group via iodination with I2 and phenyliodine(III) bis(trifluoroacetate). Reaction of the iodinated intermediate with ethylene glycol and subsequent treatment with base led to formation of the C3-acetyl chlorin. Reaction of the iodinated intermediate with ethylenediamine afforded the C3-oxiranyl chlorin. The C3-formyl chlorin was readily derived from the epoxide without hazardous reagents such as OsO4. These reactions were facile and useful alternatives to the previous methods.
authors.affiliation: Department of Material and Environmental Chemistry, Graduate School of Engineering, Utsunomiya University, Utsunomiya, Tochigi 321-8585, Japan. Electronic address: tob_p206@cc.utsunomiya-u.ac.jp.
authors.forename: Toru
authors.initials: T
authors.lastname: Oba
authors.affiliation: Department of Material and Environmental Chemistry, Graduate School of Engineering, Utsunomiya University, Utsunomiya, Tochigi 321-8585, Japan.
authors.forename: Takuto
authors.initials: T
authors.lastname: Masuya
authors.affiliation: Department of Material and Environmental Chemistry, Graduate School of Engineering, Utsunomiya University, Utsunomiya, Tochigi 321-8585, Japan.
authors.forename: Satoru
authors.initials: S
authors.lastname: Yasuda
authors.affiliation: Department of Material and Environmental Chemistry, Graduate School of Engineering, Utsunomiya University, Utsunomiya, Tochigi 321-8585, Japan.
authors.forename: Satoshi
authors.initials: S
authors.lastname: Ito
mesh_terms: D000107:Acetylation; D002734:Chlorophyll / Q000031:analogs & derivatives* / Q000138:chemical synthesis / Q000737:chemistry; D004852:Epoxy Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D054879:Halogenation; D007462:Iodobenzenes / Q000138:chemical synthesis / Q000737:chemistry; D008745:Methylation; D011166:Porphyrins / Q000138:chemical synthesis* / Q000737:chemistry; D014269:Trifluoroacetic Acid / Q000138:chemical synthesis / Q000737:chemistry
chemical_list: D004852:Epoxy Compounds; D007462:Iodobenzenes; D011166:Porphyrins; C517666:phenyliodine(III) bis(trifluoroacetate); D002734:Chlorophyll; C040298:pyropheophorbide a; C006969:chlorin; D014269:Trifluoroacetic Acid
keywords: (Bis(trifluoroacetoxy)iodo)benzene; Acetylation; Epoxidation; Formylation; Iodination; Phenyliodine bis(trifluoroacetate)