1-(2′-Anilinyl)prop-2-yn-1-ol Rearrangement for Oxindole Synthesis

Authors

  • Dr. Prasath Kothandaraman,

    1. Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University, Singapore 637371 (Singapore), Fax: (+65) 6791-1961
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  • Bing Qin Koh,

    1. Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University, Singapore 637371 (Singapore), Fax: (+65) 6791-1961
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  • Dr. Taweetham Limpanuparb,

    1. Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University, Singapore 637371 (Singapore), Fax: (+65) 6791-1961
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  • Prof. Dr. Hajime Hirao,

    Corresponding author
    1. Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University, Singapore 637371 (Singapore), Fax: (+65) 6791-1961
    • Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University, Singapore 637371 (Singapore), Fax: (+65) 6791-1961
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  • Prof. Dr. Philip Wai Hong Chan

    Corresponding author
    1. Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University, Singapore 637371 (Singapore), Fax: (+65) 6791-1961
    • Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University, Singapore 637371 (Singapore), Fax: (+65) 6791-1961
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Abstract

A synthetic method that relies on NIS (N-iodosuccinimide)-mediated cycloisomerization reactions of 1-(2′-anilinyl)prop-2-yn-1-ols to gem-3-(diiodomethyl)indolin-2-ones and 2-(iodomethylene)indolin-3-ones has been developed. The reactions were shown to be chemoselective, with secondary and tertiary alcoholic substrates exclusively giving the 3- and 2-oxindole products, respectively. In the case of the latter, the transformation features an unprecedented double 1,2-OH and 1,2-alkyl migration relay. Density functional theory (DFT) calculations based on proposed iodoaminocyclization species provide insight into this unique divergence in product selectivity.

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