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Xue H, Jiang D, Jiang H, et al. Mechanistic insights into bicyclic guanidine-catalyzed reactions from microscopic and macroscopic perspectives. J Org Chem. 2015;80(11):5745-52doi: 10.1021/acs.joc.5b00709.
Xue, H., Jiang, D., Jiang, H., Kee, C. W., Hirao, H., Nishimura, T., Wong, M. W., & Tan, C. H. (2015). Mechanistic insights into bicyclic guanidine-catalyzed reactions from microscopic and macroscopic perspectives. The Journal of organic chemistry, 80(11), 5745-52. https://doi.org/10.1021/acs.joc.5b00709
Xue, Hansong, et al. "Mechanistic insights into bicyclic guanidine-catalyzed reactions from microscopic and macroscopic perspectives." The Journal of organic chemistry vol. 80,11 (2015): 5745-52. doi: https://doi.org/10.1021/acs.joc.5b00709
Xue H, Jiang D, Jiang H, Kee CW, Hirao H, Nishimura T, Wong MW, Tan CH. Mechanistic insights into bicyclic guanidine-catalyzed reactions from microscopic and macroscopic perspectives. J Org Chem. 2015 Jun 05;80(11):5745-52. doi: 10.1021/acs.joc.5b00709. Epub 2015 May 22. PMID: 25974273.
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J Org Chem. 2015 Jun 05;80(11):5745-52. doi: 10.1021/acs.joc.5b00709. Epub 2015 May 22.

Mechanistic insights into bicyclic guanidine-catalyzed reactions from microscopic and macroscopic perspectives.

The Journal of organic chemistry

Hansong Xue, Danfeng Jiang, Huan Jiang, Choon Wee Kee, Hajime Hirao, Takahiro Nishimura, Ming Wah Wong, Choon-Hong Tan

Affiliations

  1. †Department of Chemistry and Biological Chemistry, Nanyang Technological University, 21 Nanyang Link, Singapore 637371.
  2. §Department of Chemistry, Kyoto University, Sakyo-ku, Kyoto 6068502, Japan.
  3. ‡Department of Chemistry, National University of Singapore, 3 Science Drive 3, Singapore 117543.

PMID: 25974273 DOI: 10.1021/acs.joc.5b00709

Abstract

Chiral bicyclic guanidine can act as an efficient chiral Brønsted base catalyst in enantioselective reactions, delivering good yields with high enantioselectivities. There is interest in understanding the detailed mechanisms of these guanidine-catalyzed reactions. Herein, we performed a detailed kinetic study of three different types of chiral bicyclic guanidine-catalyzed reactions, determining the bifunctionality of our guanidine catalyst. Although these three reactions share a similar catalytic cycle, their intrinsic kinetic behaviors are significantly different from each other because of the difference in the rate-determining step. The calculated theoretical rate expression for each reaction, as a result of the mechanism elucidated with density functional theory calculations, agrees well with the respective experimentally observed rate equation.

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