Journal
CHEMISTRY-A EUROPEAN JOURNAL
Volume 25, Issue 25, Pages 6342-6348Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.201900295
Keywords
alkynes; azides; cycloaddition; density functional calculations; reaction mechanisms
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Funding
- Netherlands Organization for Scientific Research (NWO)
- National Institutes of Health
- National Institutes of General Medical Sciences [GM-109078]
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The reactivities of 2-butyne, cycloheptyne, cyclooctyne, and cyclononyne in the 1,3-dipolar cycloaddition reaction with methyl azide were evaluated through DFT calculations at the M06-2X/6-311++ G(d)//M06-2X/6-31+ G(d) level of theory. Computed activation free energies for the cycloadditions of cycloalkynes are 16.5-22.0 kcalmol(-1) lower in energy than that of the acyclic 2-butyne. The strained or predistorted nature of cycloalkynes is often solely used to rationalize this significant rate enhancement. Our distortion/in-teraction-activation strain analysis has been revealed that the degree of geometrical predistortion of the cycloalkyne ground-state geometries acts to enhance reactivity compared with that of acyclic alkynes through three distinct mechanisms, not only due to (i) a reduced strain or distortion energy, but also to (ii) a smaller HOMO-LUMO gap, and (iii) an enhanced orbital overlap, which both contribute to more stabilizing orbital interactions.
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