Get access

Origin of Chemoselectivity of TMP Zincate Bases and Differences between TMP Zincate and Alkyl Lithium Reagents: A DFT Study on Model Systems

Authors

  • Masanobu Uchiyama Prof. Dr.,

    1. Graduate School of Pharmaceutical Sciences, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033, Japan
    2. “Synthesis and Control”, PRESTO, Japan Science and Technology Agency (JST), Japan, Fax: (+81) 48-467-2879
    3. Advanced Elements Chemistry Laboratory, The Institute of Physical and Chemical Research, RIKEN, 2-1 Hirosawa, Wako-shi, Saitama 351-0198, Japan
    Search for more papers by this author
  • Yotaro Matsumoto,

    1. Graduate School of Pharmaceutical Sciences, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033, Japan
    2. “Synthesis and Control”, PRESTO, Japan Science and Technology Agency (JST), Japan, Fax: (+81) 48-467-2879
    Search for more papers by this author
  • Shinya Usui,

    1. Institute of Molecular and Cellular Biosciences, The University of Tokyo, 1-1-1 Yayoi, Bunkyo-ku, Tokyo 113-0032, Japan
    2. Advanced Elements Chemistry Laboratory, The Institute of Physical and Chemical Research, RIKEN, 2-1 Hirosawa, Wako-shi, Saitama 351-0198, Japan
    Search for more papers by this author
  • Yuichi Hashimoto Prof. Dr.,

    1. Institute of Molecular and Cellular Biosciences, The University of Tokyo, 1-1-1 Yayoi, Bunkyo-ku, Tokyo 113-0032, Japan
    Search for more papers by this author
  • Keiji Morokuma Prof. Dr.

    1. Cherry L. Emerson Center for Scientific Computation and Department of Chemistry, Emory University, Atlanta, Georgia, 30322, USA
    2. Fukui Institute for Fundamental Chemistry, Kyoto University, Takano, Kyoto 606-8103, Japan
    Search for more papers by this author

  • This research was partly supported by the Astellas Foundation, the Sumitomo Foundation, and a Grant-in-Aid for Young Scientists (A) from the Ministry of Education, Culture, Sports, Science, and Technology, Japan (to M.U.). M.U. also acknowledges a Visiting Fellowship at the Cherry L. Emerson Center of Emory University and the use of its facilities. TMP=2,2,6,6-tetramethylpiperidide.

Abstract

original image

Entscheidend dafür, ob die Reaktion von Benzonitril oder Methylbenzoat mit Me2Zn(TMP)Li oder (MeLi)2 über DoM oder als 1,2-Addition verläuft, sind Übergangszustandsstrukturen wie die abgebildete. Dies ergaben Rechnungen, die sich mit den im Titel genannten Fragen befassten. TMP=2,2,6,6-Tetramethylpiperidid.

Get access to the full text of this article

Ancillary