1-(2′-Anilinyl)prop-2-yn-1-ol rearrangement for oxindole synthesis

• Main Authors: Kothandaraman, Prasath, Koh, Bing Qin, Limpanuparb, Taweetham, Hirao, Hajime, Chan, Philip Wai Hong
• Other Authors: School of Physical and Mathematical Sciences
• Format: Article
• Language: English
• Published: 2013
• Online Access: https://hdl.handle.net/10356/105286; http://hdl.handle.net/10220/16575; http://dx.doi.org/10.1002/chem.201202606
• Institution: Nanyang Technological University

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.