title: 1-(2'-Anilinyl)prop-2-yn-1-ol rearrangement for oxindole synthesis.
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.
authors.affiliation: Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University, Singapore 637371, Singapore.
authors.forename: Prasath
authors.initials: P
authors.lastname: Kothandaraman
authors.forename: Bing Qin
authors.initials: BQ
authors.lastname: Koh
authors.forename: Taweetham
authors.initials: T
authors.lastname: Limpanuparb
authors.forename: Hajime
authors.initials: H
authors.lastname: Hirao
authors.forename: Philip Wai Hong
authors.initials: PW
authors.lastname: Chan
mesh_terms: D000814:Aniline Compounds / Q000737:chemistry*; D002384:Catalysis; D003500:Cyclization; D007211:Indoles / Q000138:chemical synthesis* / Q000737:chemistry*; D015394:Molecular Structure; D000078183:Oxindoles; D011789:Quantum Theory; D013237:Stereoisomerism; D013388:Succinimides / Q000138:chemical synthesis* / Q000737:chemistry*
chemical_list: C583691:1-(2'-anilinyl)prop-2-yn-1-ol; D000814:Aniline Compounds; D007211:Indoles; D000078183:Oxindoles; D013388:Succinimides; C022960:2-oxindole; C008155:N-iodosuccinimide