New light on the mechanism of the solid state [2+2] cycloaddition of alkenes: a database analysis

FH Allen*, MF Mahon, PR Raithby, GP Shields, HA Sparkes

*Corresponding author for this work

Research output: Contribution to journalArticle (Academic Journal)peer-review

25 Citations (Scopus)

Abstract

The mechanism of the solid state [2 + 2] cycloaddition of alkenes has been investigated using the structure correlation method based on geometrical data calculated from single crystal X-ray diffraction studies retrieved from the Cambridge Structural Database (CSD). Searches were carried out for non-bonded alkene...alkene reactant interactions, within a limiting C...C separation of the sum of van der Waals radii plus 20%, and for bonded cyclobutane product fragments. The results were visualised and interpreted using principal component analysis and symmetry deformation coordinates. The reaction pathway for [2 + 2] cycloaddition was established and it was shown that ( a) the alkene moieties are not required to be parallel for the reaction to occur and (b) a large twist angle of the reacting alkene fragments is permissible to form a puckered cyclobutane reaction product, as long as similar intra-annular valence angles are maintained around the four-membered ring.

Original languageEnglish
Pages (from-to)182-187
Number of pages6
JournalNew Journal of Chemistry
Volume29
Issue number1
DOIs
Publication statusPublished - 2005

Keywords

  • SINGLE-CRYSTAL TRANSFORMATION
  • TOPOCHEMISTRY
  • ACID

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