Journal
SYNTHESIS-STUTTGART
Volume 53, Issue 10, Pages 1760-1770Publisher
GEORG THIEME VERLAG KG
DOI: 10.1055/s-0040-1706639
Keywords
halogenation; heterocycles; trichloroisocyanuric acid; ring contraction; phthalazine; phthalimide
Categories
Funding
- Basic Science Research Program through the National Research Foundation of Korea (NRF) - Ministry of Science ICT [NRF-2020R1F1A1076028]
- 'GIST Research Institute (GRI) - GIST
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An unprecedented N-chlorinative ring contraction reaction of 1,2-diazines was discovered and investigated, showing unique reactivity towards 1,4-dimethoxyphthalazine scaffold and TCICA. The assisting role of n-Bu4NCl and the use of a labile O-silyl group were identified to improve overall efficiency.
An unprecedented N-chlorinative ring contraction of 1,2-diazines was discovered and investigated with an electrophilic chlorinating reagent, trichloroisocyanuric acid (TCICA). Through optimization and mechanistic analysis, the assisting role of n-Bu4NCl as an exogenous nucleophile was identified, and the optimized reaction conditions were applied to a range of 1,4-dimethoxyphthalazine derivatives. Also, an improvement of overall efficiency was demonstrated by the use of a labile O-silyl group. A bicyclization/ring-opening mechanism, inspired by the Favorskii rearrangement, was proposed and supported by the DFT calculations. Furthermore, the efforts on scope expansion as well as the evaluation of other electrophilic promoters revealed that the newly developed ring contraction reactivity is a unique characteristic of 1,4-dimethoxyphthalazine scaffold and TCICA.
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