Theoretical Mechanistic Investigation of the Dynamic Kinetic Resolution of N-Protected Amino Acid Esters using Phase-Transfer Catalysts

  • Eiji Yamamoto
    Department of Chemistry, Graduate School of Science, Kyushu University, Fukuoka 819-0395, Japan
  • Kaoru Kobayashi
    Department of Chemistry, Graduate School of Science, Kyushu University, Fukuoka 819-0395, Japan
  • Kodai Wakafuji
    Department of Chemistry, Graduate School of Science, Kyushu University, Fukuoka 819-0395, Japan
  • Takashi Kamachi
    Department of Life, Environment and Applied Chemistry, Fukuoka Institute of Technology, 3-30-1 Wajiro-higashi, Higashi-ku, Fukuoka 811-0295, Japan
  • Makoto Tokunaga
    Department of Chemistry, Graduate School of Science, Kyushu University, Fukuoka 819-0395, Japan

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説明

A detailed theoretical mechanistic investigation on the dynamic kinetic resolution of N-protected amino acid esters using phase-transfer catalysts is described. Semiautomatic exhaustive conformation search of transition state (TS)-like structures were carried out using the ConFinder program and the pseudo-TS conformational search (PTSCS) method. This conformational search method successfully provided reasonable TS structures for determining the stereoselectivity in the asymmetric base hydrolysis of hexafluoroisopropyl (HFIP) esters as well as the racemization mechanism. Furthermore, the independent gradient model (IGM) analysis of the TS structures suggested that the H-bonding interactions with the oxyanion hole and π-stacking interactions are the common important features of the proposed TS structures that determine the stereoselectivity.

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