Stereoselective reduction,methylation, and phenylation of the 13-carbonyl group in chlorophyll derivatives |
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Authors: | Hitoshi Tamiaki Rie Monobe Shun Koizumi Tomohiro Miyatake Yusuke Kinoshita |
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Institution: | 1. Graduate School of Life Sciences, Ritsumeikan University, Kusatsu, Shiga 525-8577, Japan;2. Department of Materials Chemistry, Faculty of Science and Technology, Ryukoku University, Otsu, Shiga 520-2194, Japan |
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Abstract: | Regioselective reduction of the 13-carbonyl group on the five-membered exo-ring of methyl pyropheophorbide-a, one of the chlorophyll-a derivatives, with sodium borohydride gave an epimeric mixture of (131R/S)-hydroxy-chlorins. The stereoselectivity was controlled by the steric effect of the (17S)-methoxycarbonylethyl group to afford the (131S)-rich secondary alcohol (25% de). The use of sterically large lithium tri(sec-butyl)borohydride as the reductant enhanced the stereoselectivity to 55% de. The regio- and stereoselective methylation and phenylation of the 13-C O of pyropheophorbide-a were observed using methyl and phenyl lithium, respectively. The major diastereomer of the tertiary alcohols obtained had the same configuration at the 131-stereogenic center as in the reduced product. All of the anion species (H?, CH3?, and C6H5?) favorably attacked the 131-carbon atom from the reverse side of the 17-propionate residue, that is, the less sterically crowded face of the 13-C O plane. |
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