Theoretical study of keto-enol tautomerism in 7-epi-clusianone by quantum chemical calculations of NMR chemical shifts

被引：1

作者：

de Albuquerque, Ana Carolina F. ^{[1
]}

Correa, Guilherme S. ^{[1
]}

Albuquerque, Gustavo T. ^{[1
]}

Costa, Fabio Luiz P. ^{[2
]}

Costa, Luciano T. ^{[3
]}

Lage, Mateus R. ^{[4
,5
]}

Carneiro, Jose Walkimar de M. ^{[6
]}

Junior, Fernando Martins dos S. ^{[1
]}

机构：

[1] Fluminense Fed Univ UFF, Chem Inst, Dept Organ Chem, BR-24020141 Niteroi, RJ, Brazil

[2] Fed Univ Jatai UFJ, Chem Inst, BR 364 Km 195, BR-75801615 Jatai, Go, Brazil

[3] Fluminense Fed Univ UFF, Chem Inst, Dept Phys Chem, BR-24020141 Niteroi, RJ, Brazil

[4] Fed Univ Maranhao UFMA, Campus Balsas,MA-140,Km 04, BR-65800000 Balsas, MA, Brazil

[5] Fed Univ Maranhao UFMA, Ctr Social Sci Hlth & Technol, Grad Program Mat Sci, Rua Urbano Santos 1734, BR-65900410 Imperatriz, MA, Brazil

[6] Fluminense Fed Univ UFF, Chem Inst, Dept Inorgan Chem, BR-24020141 Niteroi, RJ, Brazil

来源：

JOURNAL OF MOLECULAR MODELING | 2022年 / 28卷 / 08期

关键词：

Tautomerism; Natural products; DFT; Nuclear magnetic resonance; DP4+; BENZOPHENONE; 7-EPICLUSIANONE; FRUITS; H-1;

D O I：

10.1007/s00894-022-05234-4

中图分类号：

Q5 [生物化学]; Q7 [分子生物学];

学科分类号：

071010 ; 081704 ;

摘要：

Plants from the Garcinia genus have been used worldwide due to their therapeutic properties. Among the various metabolites isolated from this genus, 7-epi-clusianone, a tetraprenylated benzophenone, stands out for its wide range of identified biological activities. This benzophenone can exist in five tautomeric forms, although the benzene-d(6) and chloroform-d(3) solution nuclear magnetic resonance (NMR) spectra revealed only two tautomeric forms (B and C) in equilibrium, with concentration ratio depending on the solvent in which the spectrum was obtained. Calculated energy values suggested that tautomeric forms B and E would be prevalent in benzene-d(6) solution, in contrast to the experimental data. Considering this conflicting result, we employed the statistical DP4 + method based on C-13 and H-1 NMR chemical shift calculations, in the gas phase and in benzene-d(6) solution, to confirm that the B and C tautomeric forms of 7-epi-clusianone are the most prevalent in the experimental conditions.

引用

页数：6

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