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Volumn 132, Issue 36, 2010, Pages 12660-12667

Oxygen superbases as polar binding pockets in nonpolar solvents

Author keywords

[No Author keywords available]

Indexed keywords

BINDING POCKETS; BIPYRIDYL; FREE BASIS; NON-POLAR SOLVENTS; OXYGEN ATOM; POLARIZED TRANSITION; PROTON AFFINITY; SUPERBASES;

EID: 77956438198     PISSN: 00027863     EISSN: 15205126     Source Type: Journal    
DOI: 10.1021/ja103744f     Document Type: Article
Times cited : (23)

References (67)
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    • Wong, O.A.1    Shi, Y.2
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    • et al., revision A.02; Gaussian, Inc.: Wallingford, CT.
    • Frisch, M. J.; et al. Gaussian 09, revision A.02; Gaussian, Inc.: Wallingford, CT, 2009.
    • (2009) Gaussian 09
    • Frisch, M.J.1
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    • RSC Theoretical and Computational Chemistry Series, No. 2; Royal Society of Chemistry: Cambridge, U.K.
    • Hobza, P. and Müller-Dethlefs, K. Non-covalent Interactions: Theory and Experiment; RSC Theoretical and Computational Chemistry Series, No. 2; Royal Society of Chemistry: Cambridge, U.K., 2010.
    • (2010) Non-covalent Interactions: Theory and Experiment
    • Hobza, P.1    Müller-Dethlefs, K.2
  • 46
    • 4544352935 scopus 로고    scopus 로고
    • For insightful essays about the performance and inherent problems of the kinetic method, see
    • For insightful essays about the performance and inherent problems of the kinetic method, see: Bouchoux, G., Sablier, M., and Berruyer-Penaud, F. J. Mass Spectrom. 2004, 39, 986
    • (2004) J. Mass Spectrom. , vol.39 , pp. 986
    • Bouchoux, G.1    Sablier, M.2    Berruyer-Penaud, F.3
  • 54
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    • note
    • We also probed the collisional experiments using argon as a collision gas and using an ion-trap instrument in order to obtain data at different effective temperatures. In contrast to the exclusive dissociations of the proton-bound dimers to the protonated bases obtained in the experiments with xenon (see the SI for the spectra), the experiments with argon and in the ion trap also led to other dissociation channels, such as oxygen transfers from the N -oxide bases, so we did not include those data here.
  • 62
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    • note
    • Formally, the diatomic neutral alkaline-earth oxides (particularly CaO, SrO, and BaO) are the strongest oxygen superbases known, but they are not comparable with the organocatalysts studied here.
  • 63
    • 77956431085 scopus 로고    scopus 로고
    • note
    • 2 at -40 °C gives 68% yield with 87% ee in 12 h, and only <5% yield is observed after 12 h when the reaction is conducted at-40 °C in toluene. (32)
  • 66
    • 77956421811 scopus 로고    scopus 로고
    • note
    • The allylation of benzaldehyde with allyltrichlorosilane catalyzed by (R)- 1b (10 mol %) in PhCl (-40 °C, 1 h) without Hünig base (DIPEA) yielded only racemic product (50%). No asymmetric induction was observed.


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