Understanding the 1,3-Dipolar Cycloadditions of Allenes.

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ID: 101711
2020
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Abstract
We have quantum chemically studied the reactivity, site-, and regioselectivity of the 1,3-dipolar cycloaddition reaction between methyl azide and various allenes, including the archetypal allene propadiene, heteroallenes, and cyclic allenes, using density functional theory (DFT). The  1,3-dipolar  cycloaddition reactivity of linear (hetero)allenes decreases as the number of heteroatoms in the allene increases and the formation of the 1,5-adduct is, in all cases, favored over the 1,4-adduct, both effects find their origin from the strength of the primary orbital interactions . The cycloaddition reactivity of cyclic allenes was also investigated, and the increased predistortion of allenes,  that results upon cyclization, leads to systematically lower activation barriers not due to the expected variations in the strain energy, but instead from the differences in the interaction energy . The geometrical predistortion of cyclic allenes enhances the reactivity compared to linear allenes  through a unique mechanism that involves a smaller HOMO-LUMO gap, which manifests into more stabilizing orbital interactions .
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yu2020understandingchemistry Use this key to autocite in the manuscript while using SciMatic Manuscript Manager or Thesis Manager
Authors Yu, Song;Vermeeren, Pascal;van Dommelen, Kevin;Bickelhaupt, Matthias;Hamlin, Trevor A;
Journal Chemistry (Weinheim an der Bergstrasse, Germany)
Year 2020
DOI
10.1002/chem.202000857
URL
Keywords
1,3-dipolar cycloadditions * activation strain model * allenes * density functional theory calculations * reactivity

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