Journal article
Asmic Isocyanide [3 + 2] Cascade to Dihydrooxazoles and Dihydroimidazoles
Journal of organic chemistry, v 85(14), pp 9153-9160
17 Jul 2020
PMID: 32639153
Featured in Collection : UN Sustainable Development Goals @ Drexel
Abstract
The versatile isocyanide building block Asmic, anisylsulfanylmethylisocyanide, reacts with aldehydes and ketones in a BF3·OEt2-mediated condensation to afford thioimidoyl-substituted 2,5-dihydrooxazoles. The condensation is distinguished from related base and transition-metal-catalyzed [3 + 2] processes in proceeding via the condensation of aldehydes and ketones with 2 equiv of an isocyanide followed by a molecular rearrangement that installs four new bonds. BF3·OEt2 mediates an analogous condensation of Asmic with imines to generate N-substituted dihydroimidazoles. Mechanistically, BF3·OEt2 activates the isocyanide to facilitate deprotonation evolving to a zwitterion that traps π-electrophiles in a formal [3 + 2] process. A second deprotonation–condensation with Asmic initiates a structural rearrangement involving a sulfanyl elimination–addition transposition sequence. The resulting dihydrooxazoles and dihydroimidazoles contain a thioimidate that serves as a diversification point for further elaboration.
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Details
- Title
- Asmic Isocyanide [3 + 2] Cascade to Dihydrooxazoles and Dihydroimidazoles
- Creators
- Chepuri V. Suneel Kumar - Drexel UniversityCaleb W Holyoke - Drexel UniversityTaylor M Keller - Temple UniversityFraser F Fleming - Drexel University
- Publication Details
- Journal of organic chemistry, v 85(14), pp 9153-9160
- Publisher
- American Chemical Society; Washington, DC
- Resource Type
- Journal article
- Language
- English
- Academic Unit
- Chemistry
- Web of Science ID
- WOS:000551550500035
- Scopus ID
- 2-s2.0-85088031378
- Other Identifier
- 991019169694804721
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- Collaboration types
- Domestic collaboration
- Web of Science research areas
- Chemistry, Organic