Deuterium isotope effects on carbon-13 chemical shifts of protoadamantane. Evidence for geometrical dependence of 3.DELTA. and 4.DELTA. effects

Majerski, Zdenko; Zuanic, M.; Metelko, Biserka

doi:10.1021/ja00292a044

Cited by 38 publications

(29 citation statements)

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“…The original peak gradually shortened and a new broad peak appeared shifted to a higher field, which seemed to be due to the heavy atom effect of CHD or CD 2 on C12. [9][10][11] Figures 2A and C show changes in the signal pattern on 14 methyl protons, in which the new higher shifted signals seem to be triplet. These changes were also due to the H-D exchange reaction of CH 3 , CH 3 →CH 2 D→CHD 2 →CD 3 and signal splittings to triplet were due to a coupling with deuterium.…”

Section: Results Andmentioning

confidence: 99%

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Hydrogen-Deuterium (H-D) Exchange Reaction of Warfarin in D2O Solution

Tode

Takeuchi

Iwakawa

et al. 2009

CHEMICAL & PHARMACEUTICAL BULLETIN

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Section: Results Andmentioning

confidence: 99%

“…These observations agree with a decrease in CH 2 and the appearance of CHD and CD 2 . The higher field shift of the new signal may be due to the heavy atom effect of deuterium [9][10][11] and the quadrupole effect to broaden the signal.…”

Section: Results Andmentioning

confidence: 99%

Hydrogen-Deuterium (H-D) Exchange Reaction of Warfarin in D2O Solution

Tode

Takeuchi

Iwakawa

et al. 2009

CHEMICAL & PHARMACEUTICAL BULLETIN

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“…The I3C spectra of the recovered deuterated materials reveal the sites of HID exchange through the characteristic 'H-induced effects (11). Typically, in saturated systems, a deuterated carbon exhibits an upfield shift ('A) of 300-600 ppb Samples of Id-dx and 3d-d, were obtained from runs with I d .…”

Section: Hid Exchange Experimentsmentioning

confidence: 99%

13C magnetic resonance studies. 129. Homoenolization in the camphenilone system. Examination of some 7-substituted derivatives

Peiris¹,

Ragauskas²,

Stothers³

1987

Can. J. Chem.

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SRIYAWATHIE PEIRIS, ARTHUR J. RAGAUSKAS, and J. B. STOTHERS. Can. J. Chem. 65, 789 (1987).The behavior of the 7,7-dimethyl, 7-spirocyclopropyl, and 7-isopropylidene derivatives of camphenilone under strongly basic conditions (t-BuO-/t-BuOH/185"C) has been investigated to examine substituent effects on P-enolization in the [2.2.1] system. In each case, an equilibrium mixture of the initial ketone and its corresponding 5-substituted isomer was obtained, with the latter increasingly favored through the series. In each case the '~1 % exchange processes were examined by experiments utilizing t-BuO-/t-BuOD to establish the individual sites of deuterium incorporation in these ketones with 2H and 13c magnetic resonance. These data provide the stereoselectivities and relative rates of the exchange processes. The 'H-induced effects in the I3C spectra are discussed. SRIYAWATHIE PEIRIS, ARTHUR J. RAGAUSKAS et J. B. STOTHERS. Can. J. Chem. 65, 789 (1987) Dans le but d'kvaluer les effets des substituants sur la p-Cnolisation dans les syst$mes [2.2.1], on a CtudiC le comportement des dCrivCs dimkthyl-7,7, spirocyclopropyl-7 et isopropylidkne-7 de la camphknoline dans des conditions fortement basiques (tert-BuO-ltert-BuOH/185"C). Dans chacun des cas, on a obtenu un mClange i l'kquilibre contenant de la cttone initiale et de son isomkre correspondant substituC en position 5; la quantitC de ce dernier augmente dans la sCrie des composts CtudiCs. Dans chacun des cas, on a CtudiC les processus d'echange 'H/'H sous l'influence du tert-BuO-ltert-BuOD; on a pu Ctablir les sites individuels d'incorporation du deuterium dans ces cCtones en faisant appel A la rmn du ' H et du I3C. Ces donnCes nous ont permis d'Ctablir les stCrCosClectivitCs et les vitesses relatives des processus d'Cchange. On discute des effets du ' H sur les spectres rmn du I3C.[Traduit par la revue]

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“…[29] The relatively large magnitude of these effects (that is at least on a par with the magnitude of three-bond 13 C isotope shifts in proteins) warrants a further, more detailed investigation. 13 C four-bond deuterium isotope shifts in small conformationally constrained organic molecules have been analyzed previously, [3][4][5]7] and at least on one occasion, a very unusual four-bond deuterium isotope effect on proton chemical shifts (~150 ppb) resulting from a strong hydrogen bond between an enzyme and transition-state-analog inhibitor was observed. [36] Here, NMR measurements of the effects of 1 H-to-D substitution at several positions in a protein on the chemical shifts of backbone amide nitrogens located four bonds away are described.…”

Section: Introductionmentioning

confidence: 99%

“…4(c)) and are noticeably larger than the Earlier, 13 C four-bond deuterium isotope shifts in small organic molecules have been related primarily to 'through-space' interactions between the nucleus whose isotope shift is measured ( 13 C) and the dipole where the 1 H-to-D substitution takes place. [3][4][5]7] In the case of four-bond 15 N isotope effects characterized in a folded protein here, direct interactions of the backbone amide 15 N nucleus with the 15 N i±1 -1 H/D and 13 C β -H/D dipoles have to be considered. Clearly, any such interaction would be distance dependent.…”

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confidence: 99%

Four‐bond deuterium isotope effects on the chemical shifts of amide nitrogens in proteins

Tugarinov

2013

Magnetic Reson in Chemistry

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An approach towards precision NMR measurements of four-bond deuterium isotope effects on the chemical shifts of backbone amide nitrogen nuclei in proteins is described. Three types of four-bond (15) N deuterium isotope effects are distinguished depending on the site of proton-to-deuterium substitution: (4)ΔN(N(i-1)D), (4)ΔN(N(i+1)D) and (4)ΔN(Cβ,(i-1)D). All the three types of isotope shifts are quantified in the (partially) deuterated protein ubiquitin. The (4)ΔN(N(i+1)D) and (4)ΔN(C(β,i-1)D) effects are by far the largest in magnitude and vary between 16 and 75 ppb and -18 and 46 ppb, respectively. A semi-quantitative correlation between experimental (4)ΔN(N(i+1)D) and (4)ΔN(C(β,i-1)D) values and the distances between nitrogen nuclei and the sites of (1)H-to-D substitution is noted. The largest isotope shifts in both cases correspond to the shortest inter-nuclear distances.

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Deuterium isotope effects on carbon-13 chemical shifts of protoadamantane. Evidence for geometrical dependence of 3.DELTA. and 4.DELTA. effects

Cited by 38 publications

References 1 publication

Hydrogen-Deuterium (H-D) Exchange Reaction of Warfarin in D2O Solution

Hydrogen-Deuterium (H-D) Exchange Reaction of Warfarin in D2O Solution

13C magnetic resonance studies. 129. Homoenolization in the camphenilone system. Examination of some 7-substituted derivatives

Four‐bond deuterium isotope effects on the chemical shifts of amide nitrogens in proteins

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