2011
DOI: 10.1039/c0cp00894j
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Anomeric effect in N-azidomethylpyrrolidine: gas-phase electron diffraction and theoretical study

Abstract: Gas-phase electron-diffraction data and high-level quantum chemical calculations have been used to study the conformational behaviour of N-azidomethylpyrrolidine. The two most stable conformers with a relative abundance of about 80% at 298 K possess gauche orientation of the azidomethyl group around the C-N(pyr) bond (C-N(azido)gauche with respect to the endocyclic N(pyr)-C bond). This orientation is a strong manifestation of an anomeric effect. The influence of the anomeric effect is also reflected in shorten… Show more

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Cited by 2 publications
(4 citation statements)
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“…[ [18][19][20][21][22][23][24][25] made using GED regarding the anomeric effect in N(CH3)2(CH2F) and the theoretical work [26][27][28][29][30] in the literature regarding the anomeric effect in NH2(CH2F). A classic 'no-bond-double-bond' [18,19] resonance scheme, invoked to describe the geometric consequences of the anomeric effect in species such as N(CH3)2(CH2F) (measurably shortened and lengthened rN-C and rC-F internuclear distances, respectively, and an increase in the aN-C-F angle [18,19]) can be adapted to give the immonium-like resonance structures of Scheme 1 for A, similar to that given by Klapötke et al [1] give for the single crystal.…”
Section: Resultsmentioning
confidence: 99%
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“…[ [18][19][20][21][22][23][24][25] made using GED regarding the anomeric effect in N(CH3)2(CH2F) and the theoretical work [26][27][28][29][30] in the literature regarding the anomeric effect in NH2(CH2F). A classic 'no-bond-double-bond' [18,19] resonance scheme, invoked to describe the geometric consequences of the anomeric effect in species such as N(CH3)2(CH2F) (measurably shortened and lengthened rN-C and rC-F internuclear distances, respectively, and an increase in the aN-C-F angle [18,19]) can be adapted to give the immonium-like resonance structures of Scheme 1 for A, similar to that given by Klapötke et al [1] give for the single crystal.…”
Section: Resultsmentioning
confidence: 99%
“…A classic 'no-bond-double-bond' [18,19] resonance scheme, invoked to describe the geometric consequences of the anomeric effect in species such as N(CH3)2(CH2F) (measurably shortened and lengthened rN-C and rC-F internuclear distances, respectively, and an increase in the aN-C-F angle [18,19]) can be adapted to give the immonium-like resonance structures of Scheme 1 for A, similar to that given by Klapötke et al [1] give for the single crystal. The anomeric effect in a range of fluorinated tertiary amines studied by Oberhammer et al [18][19][20][21][22][23][24][25] stabilizes the antiperiplanar configuration of the C-F bond with respect to the lone pair on the amine centre relative to the synperiplanar configuration, the strength of the stabilization conferred being both proportional to the orbital overlap between the C-F * orbital and the lone-pair-containing orbital on the amine centre and inversely proportional to the energy difference between the two orbitals [18]. Oberhammer et al consequently report observing only the antiperiplanar configuration for species such as N(CH3)2(CH2F) and N(CH3)2(CF3) [18,19] in the gas phase.…”
Section: Resultsmentioning
confidence: 99%
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