P-9 9位修飾レチナール誘導体のダイバージェント合成(ポスター発表の部)

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概要

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• It has been established that the trigger process of retinal proteins is a regioselective photoisomerization of retinal linked with retinal proteins. Recently, it was suggested that an interaction between the methyl groups on retinal side chain (C-9 and C-13) and the amino acid residues near by retinal played an crucial role in the function of retinal proteins. Therefore, it was anticipated that 9-functionalized retinal derivatives would be an useful tool for the investigation of mechanistic details of this important interaction. Although a great variety of synthetic retinals have been reported, the synthesis focusing on functionalization at the C-9 has not been extensively examined. We describe here a divergent synthesis of 9-functionalized retinal derivatives based on the use of C4+X unit as the key synthetic unit. The stereoselective synthesis of C4+X units bearing Cl, Br, and I were successfully employed by the application of addition reaction of lithium halide to 1, while the addition of fluorine nucleophiles (CsF, KF) were ineffective. According to the head-to-tail chain elongation, C4+X units 2a-c were subjected to a series of coupling reactions with C_<10> ylide 6 and C_5 phosphonate 10 to give the corresponding 9-Cl, Br, and I-retinoates 11a-c. Reduction of 11a-c with DIBAL followed by oxidation with MnO_2, afforded 9-Cl, Br, and I-retinals 13a-c as a 5:4 mixture of 13-trans- and cis-isomers. The synthesis of 9-F-retinal 24 was furnished by the alternative linkage of C4+X unit 20 using the Stille's cross coupling reaction. Horner-Emmons olefination of 15 with 16 gave 4-cis-18 as a single isomer. Reduction of 18 followed by the cross coupling reaction with 20 yielded 2,6-dicis-21, which underwent regioselective isomerization with a catalytic amount of iodine to give 6-trans-21. According to the similar manipulations as described above, 21 was converted into 13-cis-9-F-retinal 24. The regioselective isomerization of 13-cis-24 to the trans-24 was achieved by acid catalyzed isomerization using trifluoroacetic acid. Incorporation of these new retinal derivatives with bacterioopsin gave their bacteriorhodopsin analogs, respectively. These absorption maxima and opsin-shift values were similar to these of bacteriorhodopsin.

• 天然有機化合物討論会の論文
• 1995-09-01

著者

• 吉原 和雄

  サントリー生有研

• 関谷 紀子

  (財)サントリー生物有機化学研究所

• 吉原 和雄

  (財)サントリー生物有機化学研究所

• 品田 哲朗

  サントリー生有研

• 品田 哲郎

  財・サントリー生有研

• 関谷 紀子

  財・サントリー生有研

• 吉原 和雄

  財・サントリー生有研

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