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Bimolecular nature of boron trifluoride catalyzed glycosylation of a galactosyl donor: The role of the acceptor

Authors

  • Haichen Li,

    1. College of Chemistry, Nankai University, Tianjin 300071, People's Republic of China
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  • Yuanyuan Qiao

    Corresponding author
    1. Computational Center for Molecular Science, Nankai University, Tianjin 300071, People's Republic of China
    • College of Chemistry, Nankai University, Tianjin 300071, People's Republic of China
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College of Chemistry, Nankai University, Tianjin 300071, People's Republic of China. E-mail: yuanyuanqiao@nankai.edu.cn

Abstract

Density functional theory (DFT) computations disclose the mechanism of a crucial neighboring participation step in BF3 catalyzed stereoselective glycosylation of 1,2-cyclopropaneacetylated galactosyl donor. Two tandem SN2 displacements comprise this step: first, the glycosyl acceptor attacks the BF3-activated donor to break the donor's 1,2-cyclopropane ring; then, the donor's 2-acetyl oxygen substitutes the acceptor to accomplish the neighboring participation. A donor–acceptor hydrogen bond has been found to lower the overall activation free energy. This mechanism is preferred over a 2-acetyl oxygen coface SN2 displacement mechanism, in which no glycosyl acceptor is involved. © 2013 Wiley Periodicals, Inc.

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