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Yamanaka M, Yoshida U, Sato M, et al. Origin of high E-selectivity in 4-pyrrolidinopyridine-catalyzed tetrasubstituted α,α'-alkenediol: a computational and experimental study. J Org Chem. 2015;80(6):3075-82doi: 10.1021/jo5029453.
Yamanaka, M., Yoshida, U., Sato, M., Shigeta, T., Yoshida, K., Furuta, T., & Kawabata, T. (2015). Origin of high E-selectivity in 4-pyrrolidinopyridine-catalyzed tetrasubstituted α,α'-alkenediol: a computational and experimental study. The Journal of organic chemistry, 80(6), 3075-82. https://doi.org/10.1021/jo5029453
Yamanaka, Masahiro, et al. "Origin of high E-selectivity in 4-pyrrolidinopyridine-catalyzed tetrasubstituted α,α'-alkenediol: a computational and experimental study." The Journal of organic chemistry vol. 80,6 (2015): 3075-82. doi: https://doi.org/10.1021/jo5029453
Yamanaka M, Yoshida U, Sato M, Shigeta T, Yoshida K, Furuta T, Kawabata T. Origin of high E-selectivity in 4-pyrrolidinopyridine-catalyzed tetrasubstituted α,α'-alkenediol: a computational and experimental study. J Org Chem. 2015 Mar 20;80(6):3075-82. doi: 10.1021/jo5029453. Epub 2015 Feb 26. PMID: 25674925.
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J Org Chem. 2015 Mar 20;80(6):3075-82. doi: 10.1021/jo5029453. Epub 2015 Feb 26.

Origin of high E-selectivity in 4-pyrrolidinopyridine-catalyzed tetrasubstituted α,α'-alkenediol: a computational and experimental study.

The Journal of organic chemistry

Masahiro Yamanaka, Urara Yoshida, Makoto Sato, Takashi Shigeta, Keisuke Yoshida, Takumi Furuta, Takeo Kawabata

Affiliations

  1. †Department of Chemistry and Research Center for Smart Molecules, Faculty of Science, Rikkyo University, 3-34-1 Nishi-Ikebukuro, Toshima-ku, Tokyo 171-8501, Japan.
  2. ‡Institute for Chemical Research, Kyoto University, Uji, Kyoto 611-0011, Japan.

PMID: 25674925 DOI: 10.1021/jo5029453

Abstract

We have developed 4-pyrrolidinopyridine catalysts for the geometry-selective (E-selective) acylation of tetrasubstituted α,α'-alkenediols. To elucidate the major factors of the high geometry selectivity, experimental and computational studies were carried out. The control experiments with respect to the substituent of the substrate indicated the fundamental hydrogen bonding of the acidic hydrogen of NHNs and the Z-OH in the substrate. Comparison between C2- and C1-symmetric catalysts exhibited the necessity of the C2-symmetric catalyst structure. The computationally proposed transition state (TS) model well explained the experimental results. Whereas the fundamental NH/amide-CO and the two-point free-OH/acetate anion hydrogen bonds stabilize the transition state (TS), affording the E-product, the steric repulsion between the N-protecting group and the amide side chain destabilizes TS, affording the Z-product. The role of the two amide side chains of the catalyst in a C2-symmetric fashion is the enhancement of the molecular recognition ability through the additional hydrogen bond in a cooperative manner.

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