NHC Organocatalytic Formal LUMO Activation of α,β-Unsaturated Esters for Reaction with Enamides†
Dr. Jiajia Cheng
Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University, Singapore 637371 (Singapore) http://www.ntu.edu.sg/home/robinchi
Search for more papers by this authorZhijian Huang
Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University, Singapore 637371 (Singapore) http://www.ntu.edu.sg/home/robinchi
Search for more papers by this authorCorresponding Author
Prof. Dr. Yonggui Robin Chi
Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University, Singapore 637371 (Singapore) http://www.ntu.edu.sg/home/robinchi
Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University, Singapore 637371 (Singapore) http://www.ntu.edu.sg/home/robinchiSearch for more papers by this authorDr. Jiajia Cheng
Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University, Singapore 637371 (Singapore) http://www.ntu.edu.sg/home/robinchi
Search for more papers by this authorZhijian Huang
Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University, Singapore 637371 (Singapore) http://www.ntu.edu.sg/home/robinchi
Search for more papers by this authorCorresponding Author
Prof. Dr. Yonggui Robin Chi
Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University, Singapore 637371 (Singapore) http://www.ntu.edu.sg/home/robinchi
Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University, Singapore 637371 (Singapore) http://www.ntu.edu.sg/home/robinchiSearch for more papers by this authorWe thank the Singapore National Research Foundation (NRF), the Singapore Economic Development Board (EDB), GlaxoSmithKline (GSK), and Nanyang Technological University (NTU) for generous financial support, and Dr. Y. Li and Dr. R. Ganguly (NTU) for X-ray crystal-structure analysis. LUMO=lowest unoccupied molecular orbital, NHC=N-heterocyclic carbene.
Graphical Abstract
An effective wake-up call: Stable α,β-unsaturated esters were activated by the addition of a chiral N-heterocyclic carbene (NHC) organocatalyst, and the resulting reactive Michael acceptor intermediates reacted with enamide nucleophiles to furnish optically pure products (see scheme; Ts=p-toluenesulfonyl). These products can be converted readily into bioactive δ-lactams, piperidines, and their derivatives.
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