1,3-Diethynylbicyclo[1.1.1]pentane, a Useful Molecular Building Block

KALETA, Jiří, Marek NEČAS and Ctibor MAZAL. 1,3-Diethynylbicyclo[1.1.1]pentane, a Useful Molecular Building Block. European Journal of Organic Chemistry. vol. 2012, No 25, p. 4783-4796. ISSN 1434-193X. doi:10.1002/ejoc.201200351. 2012.

Basic information

• Original name: 1,3-Diethynylbicyclo[1.1.1]pentane, a Useful Molecular Building Block
• Authors: KALETA, Jiří (203 Czech Republic, belonging to the institution), Marek NEČAS (203 Czech Republic, belonging to the institution) and Ctibor MAZAL (203 Czech Republic, guarantor, belonging to the institution).
• Edition: European Journal of Organic Chemistry, 2012, 1434-193X.

Other information

• Original language: English
• Type of outcome: Article in a journal
• Field of Study: 10401 Organic chemistry
• Country of publisher: Germany
• Confidentiality degree: is not subject to a state or trade secret
• WWW: URL
• Impact factor: Impact factor: 3.344
• RIV identification code: RIV/00216224:14310/12:00064414
• Organization unit: Faculty of Science
• Doi: http://dx.doi.org/10.1002/ejoc.201200351
• UT WoS: 000307937800014
• Keywords in English: Alkynes; Cross coupling; Umpolung; Small ring systems; Rod-like molecules
• Tags: AKR, rivok

Abstract

1,3-Diethynylbicyclo[1.1.1]pentane (DEBCP) has been found to be a valuable molecular building block mostly for the synthesis of extended, rigid, rod-like molecules. With its straightforward linear geometry, DEBCP can be used as a nonconjugated alternative to more frequently used pi-conjugated, rod-like building blocks. Examples of reactions that introduce DEBCP into larger structures are (1) the reaction of DEBCP lithium acetylides with electrophiles such as TMSCl, CO2, and Ph2PCl, (2) Sonogashira–Hagihara cross-coupling reactions with aryl or heteroaryl iodides or bromides, and (3) umpolung reactions that afford the corresponding dibromo and diiodo derivatives of DEBCP, which then successfully react with tert-C-cuprates derived from p- and m-dicarbadodecaboranes or bicyclopentanes. These umpolung reactions afforded a new class of molecular rods that combine carborane or bicyclo[1.1.1]pentane cages with ethynylene linkers. Many of the DEBCP derivatives were studied by single-crystal X-ray diffraction. They form well-organized arrays of molecular rotors, the DEBCP units, and so can be considered as examples of artificial molecular-size machines.

Links

• ED1.1.00/02.0068, research and development project: Name: CEITEC - central european institute of technology
• MSM0021622410, plan (intention): Name: Fyzikální a chemické vlastnosti pokročilých materiálů a struktur

Investor: Ministry of Education, Youth and Sports of the CR, Physical and chemical properties of advanced materials and structures