Synthesis of new cyano-substituted analogues of Tröger's bases from bromo-derivatives. A stereochemical dependence of long-range (n JHH , n = 4, 5, and 6) proton-proton and proton-carbon (n JCH , n = 1, 2, 3, 4, and 5) coupling constants of these compounds

Synthesis of new cyano-substituted analogues of Tröger's bases from bromo-derivatives. A stereochemical dependence of long-range (n JHH , n = 4, 5, and 6) proton-proton and proton-carbon (n JCH , n = 1, 2, 3, 4, and 5) coupling constants of these compounds

© 2019 John Wiley & Sons, Ltd.

Détails bibliographiques
Publié dans:Magnetic resonance in chemistry : MRC. - 1985. - 57(2019), 7 vom: 01. Juli, Seite 423-454
Auteur principal: Dusso, Diego (Auteur)
Autres auteurs: Ramirez, Cristina, Parise, Alejandro, Lanza, P, Vera, D Mariano, Chesta, Carlos, Moyano, E Laura, Akhmedov, Novruz G
Format: Article en ligne
Langue:English
Publié: 2019
Accès à la collection:Magnetic resonance in chemistry : MRC
Sujets:Journal Article Research Support, Non-U.S. Gov't CIGARAD EXSIDE GIAO PSYCHE Tröger's bases bsHSQCNOESY cyanation microwaves
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245 1 0 |a Synthesis of new cyano-substituted analogues of Tröger's bases from bromo-derivatives. A stereochemical dependence of long-range (n JHH , n = 4, 5, and 6) proton-proton and proton-carbon (n JCH , n = 1, 2, 3, 4, and 5) coupling constants of these compounds 
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500 |a Date Completed 17.09.2019 
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500 |a Citation Status PubMed-not-MEDLINE 
520 |a © 2019 John Wiley & Sons, Ltd. 
520 |a A free-catalyst microwave-assisted cyanation of brominated Tröger's base derivatives (2a-f) is reported. The procedure is simple, efficient, and clean affording the nitrile compounds (3a-e, I) in very good yields. Complete assignment of 1 H and 13 C chemical shifts of 2a-f, I and 3a-d, I was achieved using gradient selected 1D nuclear magnetic resonance (NMR) techniques (1D zTOCSY, PSYCHE, DPFGSE NOE, and DEPT), homonuclear 2D NMR techniques (gCOSY and zTOCSY), and heteronuclear 2D NMR techniques (gHSQCAD/or pure-shift gHSQCAD, gHMBCAD, bsHSQCNOESY, and gHSQCAD-TOCSY) with adiabatic pulses. Determination of the long-range proton-proton coupling constants n JHH (n = 4, 5, 6) was accomplished by simultaneous irradiation of two protons at appropriate power levels. In turn, determined coupling constants were tested by an iterative simulation program by calculating the 1 H NMR spectrum and comparing it to the experimental spectrum. The excitation-sculptured indirect-detection experiment (EXSIDE) and 1 H-15 N CIGARAD-HMBC (constant time inverse-detection gradient accordion rescaled heteronuclear multiple bond correlation) were applied for determination of long-range carbon-proton coupling constants n JCH (n = 2, 3, and 4) and for assignment of 15 N chemical shift at natural abundance, respectively. DFT/B3LYP optimization studies were performed in order to determine the geometry of 2c using 6-31G(d,p), 6-311G(d,p), and 6-311 + G(d,p) basis sets. For calculation of 1 H and 13 C chemical shifts, n JHH (n = 2, 3, 4, 5, and 6), and n JCH (n = 1, 2, 3, and 4) coupling constants, the GIAO method was employed at the B3LYP/6-31G(d,p), B3LYP/6-31+G(d,p), B3LYP/6-311+G(d,p), B3LYP/6-311++G(2d,2p), B3LYP/cc-pVTZ), and B3LYP/aug-cc-pVTZ) levels of theory. For the first time, a stereochemical dependence magnitude of the long-range n JHH (n = 4, 5, and 6) and n JCH (n = 1, 2, 3, 4, and 5) have been found in bromo-substituted analogues of Tröger's bases 
650 4 |a Journal Article 
650 4 |a Research Support, Non-U.S. Gov't 
650 4 |a CIGARAD 
650 4 |a EXSIDE 
650 4 |a GIAO 
650 4 |a PSYCHE 
650 4 |a Tröger's bases 
650 4 |a bsHSQCNOESY 
650 4 |a cyanation 
650 4 |a microwaves 
700 1 |a Ramirez, Cristina  |e verfasserin  |4 aut 
700 1 |a Parise, Alejandro  |e verfasserin  |4 aut 
700 1 |a Lanza, P  |e verfasserin  |4 aut 
700 1 |a Vera, D Mariano  |e verfasserin  |4 aut 
700 1 |a Chesta, Carlos  |e verfasserin  |4 aut 
700 1 |a Moyano, E Laura  |e verfasserin  |4 aut 
700 1 |a Akhmedov, Novruz G  |e verfasserin  |4 aut 
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773 1 8 |g volume:57  |g year:2019  |g number:7  |g day:01  |g month:07  |g pages:423-454 
856 4 0 |u http://dx.doi.org/10.1002/mrc.4872  |3 Volltext 
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