Interunit, through-space 1H-19F and 13-19F spin-spin couplings of 5-fluorinated arbekacins

Miyake, T.; Koyama, Yoshiko

doi:10.1016/0008-6215(94)84071-7

Cited by 7 publications

(4 citation statements)

References 15 publications

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“…NMR Spectroscopy. NMR spectra were recorded with a 5-mm 13 C/ 1 H/ 19 F triple-resonance probe or a 5-mm inverse probe, operating at 500.13 MHz for 1 H and 125.77 MHz for 13 C, and the sample temperature was maintained at 30 °C. Chemical shifts (δ) were reported in ppm relative to internal tetramethylsilane.…”

Section: Methodsmentioning

confidence: 99%

Pholipeptin, a Novel Cyclic Lipoundecapeptide from Pseudomonas fluorescens

Miyake

Iinuma

et al. 1997

J. Org. Chem.

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An inhibitor of phosphatidylinositol-specific phospholipase C (PI-PLC), pholipeptin (1), was purified from the culture broth of Pseudomonas sp. by solvent extraction and column chromatography. Acid hydrolysis of 1 gave Leu, Ile, Ser, Thr, and Asp moieties. Although 1 was a peptide compound, fragmentation by mild hydrolysis was not accomplished under any conditions. So, we performed the structure elucidation using various 2D NMR techniques. In the NMR studies, the addition of a small amount of trifluoroacetic acid gave relatively sharp and resolved signals, such that the structure of this novel cyclic lipodepsipeptide consisting of 11 amino acids and a 3-hydroxydecanoic acid moiety could be determined. Chirality of the constituent amino acids was analyzed by chiral HPLC, but two Asp residues could not be distinguished because they were contained as a racemic mixture. Finally, their chiralities were determined by NMR analysis of (13)C-labeled 1 into which [L-(13)C]Asp had been biosynthetically incorporated.

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Section: Methodsmentioning

confidence: 99%

Pholipeptin, a Novel Cyclic Lipoundecapeptide from Pseudomonas fluorescens

Miyake

Iinuma

et al. 1997

J. Org. Chem.

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“…[18] It was explained to be due to a direct through-space interaction between a fluorine lone-pair orbital and the σ * orbital of a sterically hindered C-H bond, where the former works as electron donor and the latter as electron acceptor. Hsee et al measured the through-space 13 [19] J TS CF = 5541 · e −2.44d HF (4) Furthermore, the through-space 13 C- 19 F coupling was used to determine the conformation of tricarbonylchromium complexes of biphenyl derivatives [20] and of 5-fluorinated arbekacins [21] and to assign the E or Z configuration of a series of substituted trifluoromethylvinyl compounds. [22] For application in BODIPYs, Chen et al [23] used through-space 13 C-19 F coupling to study conformations of a series of 2,10-diaryl-BODIPY dyes.…”

Section: Introductionmentioning

confidence: 99%

Conformational dynamics of bis(BF₂)‐2,2′‐bidipyrrins revealed by through‐space ¹³C¹⁹F and ¹⁹F¹⁹F couplings

Xie

Yuan

Krüger

et al. 2009

Magnetic Reson in Chemistry

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The conformation of [bis-(N,N'-difluoroboryl)]-3,3'-diethyl-4,4',8,8',9,9',10,10'-octamethyl-2,2'-bidipyrrin (1) in solution was studied by analyzing the 13C-19F and 19F-19F through-space spin-spin couplings. The 1H and 13C NMR spectra were assigned on the basis of nuclear Overhauser effect spectroscopy (NOESY), heteronuclear single-quantum correlation (HSQC), and heteronuclear multiple-bond correlation (HMBC) experiments. The 19F spectrum of 1 was compared with that of 2-ethyl-1,3,5,6,7-pentamethyl-4,4-difluoro-4-bor-3a,4a-diaza-s-indacen (2). The 19F-19F through-space spin--spin coupling in 1 was thus assigned and the coupling constant was obtained by simulating the coupling patterns. The obtained conformation of 1 was compared with those of the known complexes [bis-(N,N'-difluoroboryl)]-3,3',8,8',9,9'-hexaethyl-4,4',10,10'-tetramethyl-6,6'-(4-methylphenyl)-2,2'-bidipyrrin (3)and [bis-(N,N'-difluoroboryl)]-9,9'-diethyl-4,4',8,8',10,10'-hexamethyl-3,3'-bis(methoxycarbonylethyl)-2,2'-bidipyrrin (4). The conformational dynamics of 1, 3, and 4 was surveyed by observing the temperature dependence of the through-space coupling constants between 253 and 333 K. The 13C-19F and 19F-19F through-space spin-spin couplings thus confirm similar conformations of different BisBODIPYs in solution in contrast to earlier findings in the solid state.

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“…

The fact that only compounds 1a, 1b and 2a in the series 1-3 show long-range 13 C-19 F coupling can be used to draw conclusions regarding the structures of these molecules.Through-space coupling between carbon and fluorine atoms that are forced together through geometric constraints is a wellknown phenomenon, 1-3 but it is not often used as a tool to gauge molecular conformations. [4][5][6] Here we describe such an application as applied to 3,5-diaryl-4,4-difluoro-4-bora-3a,4a-diaza-sindacene (BODIPY ® ) dyes 1-3. 7

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confidence: 99%

“…Through-space coupling between carbon and fluorine atoms that are forced together through geometric constraints is a wellknown phenomenon, 1-3 but it is not often used as a tool to gauge molecular conformations. [4][5][6] Here we describe such an application as applied to 3,5-diaryl-4,4-difluoro-4-bora-3a,4a-diaza-sindacene (BODIPY ® ) dyes 1-3. 7…”

mentioning

confidence: 99%

Through-space 13C–19F coupling can reveal conformations of modified BODIPY dyes†

Chen¹,

Reibenspies²,

Derecskei‐Kovacs³

et al. 1999

Chem. Commun.

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Interunit, through-space 1H-19F and 13-19F spin-spin couplings of 5-fluorinated arbekacins

Cited by 7 publications

References 15 publications

Pholipeptin, a Novel Cyclic Lipoundecapeptide from Pseudomonas fluorescens

Pholipeptin, a Novel Cyclic Lipoundecapeptide from Pseudomonas fluorescens

Conformational dynamics of bis(BF₂)‐2,2′‐bidipyrrins revealed by through‐space ¹³C¹⁹F and ¹⁹F¹⁹F couplings

Through-space 13C–19F coupling can reveal conformations of modified BODIPY dyes†

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Interunit, through-space 1H-19F and 13-19F spin-spin couplings of 5-fluorinated arbekacins

Cited by 7 publications

References 15 publications

Pholipeptin, a Novel Cyclic Lipoundecapeptide from Pseudomonas fluorescens

Pholipeptin, a Novel Cyclic Lipoundecapeptide from Pseudomonas fluorescens

Conformational dynamics of bis(BF2)‐2,2′‐bidipyrrins revealed by through‐space 13C19F and 19F19F couplings

Through-space 13C–19F coupling can reveal conformations of modified BODIPY dyes†

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Conformational dynamics of bis(BF₂)‐2,2′‐bidipyrrins revealed by through‐space ¹³C¹⁹F and ¹⁹F¹⁹F couplings