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Updated: Jul 5, 2025

Spatial Separation of Molecular Conformers and Clusters
Published on: January 9, 2014
Water vs. Organic Solvents: Water-Controlled Divergent Reactivity of 2-Substituted Indoles
Airu Hashidoko1, Taku Kitanosono1, Yasuhiro Yamashita1
1Department of Chemistry, School of Science, Graduate School of Science, The University of Tokyo, Tokyo, 113-0033, Japan.
Abstract:
Water is not a good solvent for most organic compounds, yet water can offer many benefits to some organic reactions, hence enriching organic chemistry. Herein, the unique divergent reactivity of 2-substituted indoles with ⋅NO sources is presented. The amount of water solvent was harnessed for a scalable, benign, and expedient synthesis of indolenine oximes, albeit with water's inability to dissolve the reactants. 2-Methoxyethyl nitrite, which has been tailored for reactions in water, empowered this protocol by enhancing the product selectivity. We further report on chemoselective transformations of the products that rely on their structural features. Our findings are expected to offer access to an underexplored chemical space. The platform is also applicable to oximinomalonate synthesis. Mechanistic studies revealed the important role of water in the reversal of stability between oxime and nitroso compounds, promoting the proton transfer.
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