Tautomeric Nature of Quinonoid 6,7-Dimethyl-7,8-dihydro-6H-pterin in Aqueous Solution: A 15N NMR Study

Wilfred L.F. Armarego, Paul Waring, Stephen Benkovic, Douglas Sammons, Ruth Inners

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Abstract

The 15N chemical shifts of N-1, N-3, N-5, and the NH2in the parent 6,7-dideuterio-5,8-dihydro-6,7-dimethylpterin, its cation, the two-electron oxidation product quinonoid 6,7-dideuterio-6,7-dimethylpterin, its cation, the rearrangement product 7-deuterio-8-hydro-6,7-dimethylpterin, and fully oxidized 6,7-dimethylpterin were assigned from the 15N NMR spectra of the pterins with the 15N isotope in N-5 (95%), N-1 (33%), N-3 (33%), and NH2 (33%) and the pterins labeled singly in the NH2 (95%). The 15N spectrum of the unstable quinonoid dihydropterin was obtained by using dilute Bicine buffer at low temperature combined with deuterium substitution at carbons 6 and 7 to slow rearrangement to the 7,8-dihydro derivative. The spectral shifts of the 15N resonances observed upon oxidation of the parent compound to the two-electron oxidation product established that the endocyclic quinonoid 6,7-dimethyl-7,8-dihydro-6H-pterin tautomer 5 is the predominant form in aqueous solution at near neutral pH. We propose that in future the structure of the quinonoid species of 7,8-dihydro-6H-pterins which are not further substituted in the pyrimidine ring should be drawn with the 2-NH2 group and an endocyclic double bond as in 5.

Original languageEnglish (US)
Pages (from-to)3706-3712
Number of pages7
JournalJournal of the American Chemical Society
Volume107
Issue number12
DOIs
StatePublished - Jan 1 1985

Fingerprint

Pterins
Cations
Nuclear magnetic resonance
Electrons
Oxidation
Deuterium
Positive ions
Isotopes
Buffers
Carbon
Chemical shift
Temperature
Substitution reactions
Derivatives
7,8-dihydropterin
pyrimidine

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Armarego, Wilfred L.F. ; Waring, Paul ; Benkovic, Stephen ; Sammons, Douglas ; Inners, Ruth. / Tautomeric Nature of Quinonoid 6,7-Dimethyl-7,8-dihydro-6H-pterin in Aqueous Solution : A 15N NMR Study. In: Journal of the American Chemical Society. 1985 ; Vol. 107, No. 12. pp. 3706-3712.
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title = "Tautomeric Nature of Quinonoid 6,7-Dimethyl-7,8-dihydro-6H-pterin in Aqueous Solution: A 15N NMR Study",
abstract = "The 15N chemical shifts of N-1, N-3, N-5, and the NH2in the parent 6,7-dideuterio-5,8-dihydro-6,7-dimethylpterin, its cation, the two-electron oxidation product quinonoid 6,7-dideuterio-6,7-dimethylpterin, its cation, the rearrangement product 7-deuterio-8-hydro-6,7-dimethylpterin, and fully oxidized 6,7-dimethylpterin were assigned from the 15N NMR spectra of the pterins with the 15N isotope in N-5 (95{\%}), N-1 (33{\%}), N-3 (33{\%}), and NH2 (33{\%}) and the pterins labeled singly in the NH2 (95{\%}). The 15N spectrum of the unstable quinonoid dihydropterin was obtained by using dilute Bicine buffer at low temperature combined with deuterium substitution at carbons 6 and 7 to slow rearrangement to the 7,8-dihydro derivative. The spectral shifts of the 15N resonances observed upon oxidation of the parent compound to the two-electron oxidation product established that the endocyclic quinonoid 6,7-dimethyl-7,8-dihydro-6H-pterin tautomer 5 is the predominant form in aqueous solution at near neutral pH. We propose that in future the structure of the quinonoid species of 7,8-dihydro-6H-pterins which are not further substituted in the pyrimidine ring should be drawn with the 2-NH2 group and an endocyclic double bond as in 5.",
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Tautomeric Nature of Quinonoid 6,7-Dimethyl-7,8-dihydro-6H-pterin in Aqueous Solution : A 15N NMR Study. / Armarego, Wilfred L.F.; Waring, Paul; Benkovic, Stephen; Sammons, Douglas; Inners, Ruth.

In: Journal of the American Chemical Society, Vol. 107, No. 12, 01.01.1985, p. 3706-3712.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Tautomeric Nature of Quinonoid 6,7-Dimethyl-7,8-dihydro-6H-pterin in Aqueous Solution

T2 - A 15N NMR Study

AU - Armarego, Wilfred L.F.

AU - Waring, Paul

AU - Benkovic, Stephen

AU - Sammons, Douglas

AU - Inners, Ruth

PY - 1985/1/1

Y1 - 1985/1/1

N2 - The 15N chemical shifts of N-1, N-3, N-5, and the NH2in the parent 6,7-dideuterio-5,8-dihydro-6,7-dimethylpterin, its cation, the two-electron oxidation product quinonoid 6,7-dideuterio-6,7-dimethylpterin, its cation, the rearrangement product 7-deuterio-8-hydro-6,7-dimethylpterin, and fully oxidized 6,7-dimethylpterin were assigned from the 15N NMR spectra of the pterins with the 15N isotope in N-5 (95%), N-1 (33%), N-3 (33%), and NH2 (33%) and the pterins labeled singly in the NH2 (95%). The 15N spectrum of the unstable quinonoid dihydropterin was obtained by using dilute Bicine buffer at low temperature combined with deuterium substitution at carbons 6 and 7 to slow rearrangement to the 7,8-dihydro derivative. The spectral shifts of the 15N resonances observed upon oxidation of the parent compound to the two-electron oxidation product established that the endocyclic quinonoid 6,7-dimethyl-7,8-dihydro-6H-pterin tautomer 5 is the predominant form in aqueous solution at near neutral pH. We propose that in future the structure of the quinonoid species of 7,8-dihydro-6H-pterins which are not further substituted in the pyrimidine ring should be drawn with the 2-NH2 group and an endocyclic double bond as in 5.

AB - The 15N chemical shifts of N-1, N-3, N-5, and the NH2in the parent 6,7-dideuterio-5,8-dihydro-6,7-dimethylpterin, its cation, the two-electron oxidation product quinonoid 6,7-dideuterio-6,7-dimethylpterin, its cation, the rearrangement product 7-deuterio-8-hydro-6,7-dimethylpterin, and fully oxidized 6,7-dimethylpterin were assigned from the 15N NMR spectra of the pterins with the 15N isotope in N-5 (95%), N-1 (33%), N-3 (33%), and NH2 (33%) and the pterins labeled singly in the NH2 (95%). The 15N spectrum of the unstable quinonoid dihydropterin was obtained by using dilute Bicine buffer at low temperature combined with deuterium substitution at carbons 6 and 7 to slow rearrangement to the 7,8-dihydro derivative. The spectral shifts of the 15N resonances observed upon oxidation of the parent compound to the two-electron oxidation product established that the endocyclic quinonoid 6,7-dimethyl-7,8-dihydro-6H-pterin tautomer 5 is the predominant form in aqueous solution at near neutral pH. We propose that in future the structure of the quinonoid species of 7,8-dihydro-6H-pterins which are not further substituted in the pyrimidine ring should be drawn with the 2-NH2 group and an endocyclic double bond as in 5.

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