Supramolecular diversity of oxabicyclo[2.2.2]octenes formed between substituted 2H-pyran-2-ones and vinyl-moiety-containing dienophiles
ID Kranjc, Krištof (Author), ID Juranovič, Amadej (Author), ID Kočevar, Marijan (Author), ID Perdih, Franc (Author)

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In Diels–Alder reactions, 2H-pyran-2-ones as dienes can yield a large variety of cycloadducts with up to four contiguous carbon stereogenic centers. Some of the potentially most useful, however difficult to prepare due to their low thermal stability, are the primary CO$_2$-containing oxabicyclo[2.2.2]octenes, which could be formed as eight distinctive isomers (two sets of regioisomers, each of these composed of four different stereoisomers). A high-pressure synthesis of such products was recently described in a few cases where vinyl-moiety-containing dienophiles were used as synthetic equivalents of acetylene. However, structures of the primary products have been so far only rarely investigated in detail. Herein, we present seven novel single-crystal X-ray diffraction structures of such cycloadducts of both stereoisomeric forms, i.e., endo and exo. Additionally, we present a single-crystal structure of a rare case of a cyclohexadiene system stable at room temperature, obtained as a secondary product upon the retro-hetero-Diels–Alder elimination of CO$_2$ under thermal conditions (microwave irradiation), during this elimination the symmetry is increased and out of eight initially possible isomers of the reactant, this number in the product is decreased to four. In oxabicyclo[2.2.2]octene compounds, centrosymmetric hydrogen bonding was found to be the predominant motif and diverse supramolecular patterns were observed due to rich variety of C–H· · · O and C–H· · · π interactions.

Keywords:Diels-Alder reaction, organic synthesis, heterocycles, hydrogen bonds, crystal structure, X-ray diffraction, high-pressure conditions, microwave-assisted reactions, aggregation, crystal architecture
Work type:Article
Typology:1.01 - Original Scientific Article
Organization:FKKT - Faculty of Chemistry and Chemical Technology
Publication status:Published
Publication version:Version of Record
Number of pages:23 str.
Numbering:Vol. 12, iss. 10, art. 1714
PID:20.500.12556/RUL-134710 This link opens in a new window
ISSN on article:2073-8994
DOI:10.3390/sym12101714 This link opens in a new window
COBISS.SI-ID:33257219 This link opens in a new window
Publication date in RUL:27.01.2022
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Shortened title:Symmetry
Publisher:Molecular Diversity Preservation International
COBISS.SI-ID:517592345 This link opens in a new window


License:CC BY 4.0, Creative Commons Attribution 4.0 International
Description:This is the standard Creative Commons license that gives others maximum freedom to do what they want with the work as long as they credit the author.
Licensing start date:17.10.2020

Secondary language

Keywords:Diels-Alderjeva reakcija, organska sinteza, heterocikli, vodikova vez, kristalna struktura


Funder:ARRS - Slovenian Research Agency
Project number:P1-0230
Name:Organska kemija: sinteza, struktura in aplikacija

Funder:ARRS - Slovenian Research Agency
Project number:P1-0175
Name:Napredna anorganska kemija

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