Diazo compounds as highly tunable reactants in 1,3-dipolar cycloaddition reactions with cycloalkynes
- 2 August 2012
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in Chemical Science
- Vol. 3 (11) , 3237-3240
- https://doi.org/10.1039/c2sc20806g
Abstract
Diazo compounds, which can be accessed directly from azides by deimidogenation, are shown to be extremely versatile dipoles in 1,3-dipolar cycloaddition reactions with a cyclooctyne. The reactivity of a diazo compound can be much greater or much less than its azide analog, and is enhanced markedly in polar-protic solvents. These reactivities are predictable from frontier molecular orbital energies. The most reactive diazo compound exhibited the highest known second-order rate constant to date for a dipolar cycloaddition with a cycloalkyne. These data provide a new modality for effecting chemoselective reactions in a biological context.Keywords
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