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

Seiji Shinkai, Akito Kawase, Osamu Manabe

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Abstract

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.

Original languageEnglish
Pages (from-to)1075-1078
Number of pages4
JournalJournal of the Chemical Society, Perkin Transactions 1
Issue number4
Publication statusPublished - Dec 1 1990

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Coenzymes
Amines
Hydrogen
Alcohols
Oxidation
Protons
Nuclear magnetic resonance
Redox reactions
Substrates
5-deazaflavin

All Science Journal Classification (ASJC) codes

  • Chemistry(all)

Cite this

Coenzyme models. Part 52. Diastereo-differentiating hydrogen transfer in 5-deazaflavin oxidation of alcohols and amines. / Shinkai, Seiji; Kawase, Akito; Manabe, Osamu.

In: Journal of the Chemical Society, Perkin Transactions 1, No. 4, 01.12.1990, p. 1075-1078.

Research output: Contribution to journalArticle

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N2 - 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.

AB - 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.

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