Supramolecular diversity of oxabicyclo[2.2.2]octenes formed between substituted 2H-pyran-2-ones and vinyl-moiety-containing dienophiles

Kranjc, Krištof (avtor), Juranovič, Amadej (avtor), Kočevar, Marijan (avtor), Perdih, Franc (avtor)

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.

• Jezik: Angleški jezik
• Ključne besede: Diels-Alder reaction, organic synthesis, heterocycles, hydrogen bonds, crystal structure, X-ray diffraction, high-pressure conditions, microwave-assisted reactions, aggregation, crystal architecture
• Vrsta gradiva: Članek v reviji
• Tipologija: 1.01 - Izvirni znanstveni članek
• Organizacija: FKKT - Fakulteta za kemijo in kemijsko tehnologijo
• Status publikacije: Objavljeno
• Različica publikacije: Objavljena publikacija
• Leto izida: 2020
• Št. strani: 23 str.
• Številčenje: Vol. 12, iss. 10, art. 1714
• PID: 20.500.12556/RUL-134710
• UDK: 547.81:547.72
• ISSN pri članku: 2073-8994
• DOI: 10.3390/sym12101714
• COBISS.SI-ID: 33257219
• Datum objave v RUL: 27.01.2022

Gradivo je del revije

• Naslov: Symmetry
• Skrajšan naslov: Symmetry
• Založnik: Molecular Diversity Preservation International
• ISSN: 2073-8994
• COBISS.SI-ID: 517592345

Licence

• Licenca: CC BY 4.0, Creative Commons Priznanje avtorstva 4.0 Mednarodna
• Povezava: http://creativecommons.org/licenses/by/4.0/deed.sl
• Opis: To je standardna licenca Creative Commons, ki daje uporabnikom največ možnosti za nadaljnjo uporabo dela, pri čemer morajo navesti avtorja.
• Začetek licenciranja: 17.10.2020

Sekundarni jezik

• Jezik: Slovenski jezik
• Ključne besede: Diels-Alderjeva reakcija, organska sinteza, heterocikli, vodikova vez, kristalna struktura

Projekti

• Financer: ARRS - Agencija za raziskovalno dejavnost Republike Slovenije
• Številka projekta: P1-0230
• Naslov: Organska kemija: sinteza, struktura in aplikacija

• Financer: ARRS - Agencija za raziskovalno dejavnost Republike Slovenije
• Številka projekta: P1-0175
• Naslov: Napredna anorganska kemija