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Cover Feature: Structural Distortion of Cycloalkynes Influences Cycloaddition Rates both by Strain and Interaction Energies (Chem. Eur. J. 25/2019)
Author(s) -
Hamlin Trevor A.,
Levandowski Brian J.,
Narsaria Ayush K.,
Houk Kendall N.,
Bickelhaupt F. Matthias
Publication year - 2019
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201900867
Subject(s) - cycloaddition , chemistry , strain (injury) , cover (algebra) , polarization (electrochemistry) , reactivity (psychology) , azide , alkyne , computational chemistry , organic chemistry , catalysis , medicine , mechanical engineering , alternative medicine , pathology , engineering
Historically, the accelerated cycloaddition reactivity of cyclic alkynes relative to acyclic alkynes has been solely attributed to strain and these reactions have been accordingly called strain‐promoted azide–alkyne cycloadditions (SPAAC). Based on state‐of‐the‐art quantum chemical analyses, this work shows that, instead, an alternative electronic mechanism can become the decisive factor behind this acceleration, namely: an enhanced orbital interaction that stems from both a destabilization and favorable polarization of the cycloalkyne HOMO towards the azide. More information can be found in the Full Paper by K. N. Houk, F. M. Bickelhaupt, et al. on page 6342.