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Highly Electron-Deficient Pyridinium-Nitrones for Rapid and Tunable Inverse-Electron-Demand Strain-Promoted Alkyne-Nitrone Cycloaddition.

Authors :
Gunawardene PN
Luo W
Polgar AM
Corrigan JF
Workentin MS
Source :
Organic letters [Org Lett] 2019 Jul 19; Vol. 21 (14), pp. 5547-5551. Date of Electronic Publication: 2019 Jun 28.
Publication Year :
2019

Abstract

Highly accelerated inverse-electron-demand strain-promoted alkyne-nitrone cycloaddition (IED SPANC) between a stable cyclooctyne (bicyclo[6.1.0]nonyne (BCN)) and nitrones delocalized into a C <subscript> α </subscript> -pyridinium functionality is reported, with the most electron-deficient "pyridinium-nitrone" displaying among the most rapid cycloadditions to BCN that is currently reported. Density functional theory (DFT) and X-ray crystallography are explored to rationalize the effects of N - and C <subscript> α </subscript> -substituent modifications at the nitrone on IED SPANC reaction kinetics and the overall rapid reactivity of pyridinium-delocalized nitrones.

Details

Language :
English
ISSN :
1523-7052
Volume :
21
Issue :
14
Database :
MEDLINE
Journal :
Organic letters
Publication Type :
Academic Journal
Accession number :
31251633
Full Text :
https://doi.org/10.1021/acs.orglett.9b01863