Coenzyme models. Part 52. Diastereo-differentiating hydrogen transfer in 5-deazaflavin oxidation of alcohols and amines

Seiji Shinkai, Akito Kawase, Osamu Manabe

研究成果: ジャーナルへの寄稿学術誌査読

1 被引用数 (Scopus)

抄録

5-Deuteriated 5-deazaflavinophanes (dFl(n)D) were synthesized in which N-3 in the isoalloxazine group and O-2′ in the 10-(2-hydroxyphenyl) group were linked by a -(CH2)n-chain (n = 8 and 10). 1H NMR studies established that NaBH4 reduction of dFl(8)D to the reduced form dFlred(8)D, in which ring inversion is inhibited because of a short (CH2) 8 strap, gives an axial C-5 proton (Hax). This indicates that hydrogen is exclusively incorporated into the axial C-5 position. In contrast, NaBH4 reduction of dFl(10)D to dFl red(10)D, in which ring inversion is allowed because of a long (CH2)10 strap, gave an axial and an equatorial proton (Hax and Heq) in the ratio 1:1. This indicates that hydrogen is primarily incorporated into the axial C-5 position but is rapidly exchanged through ring inversion. Oxidation of alcohols and amines by dFl(n)D gave 1H NMR spectra similar to those obtained after NaBH4 reduction. Therefore we conclude that hydrogen from these substrates is also transferred to the axial C-5 position. The 'axial preference', which is generally observed for 5-deazaflavin-mediated redox reactions, was rationalized in terms of the stereoelectronic effect.

本文言語英語
ページ(範囲)1075-1078
ページ数4
ジャーナルJournal of the Chemical Society, Perkin Transactions 1
4
DOI
出版ステータス出版済み - 1990
外部発表はい

!!!All Science Journal Classification (ASJC) codes

  • 化学 (全般)

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