Regiochemical Control in Triptycene Formation-An Exercise in Subtle Balancing Multiple Factors

Lamm J-H, Vishnevskiy Y, Ziemann E, Neumann B, Stammler H-G, Mitzel NW (2018)
ChemistryOpen 7(1): 111-114.

Zeitschriftenaufsatz | Veröffentlicht | Englisch
 
Download
OA 720.38 KB
Abstract / Bemerkung
Reactions between 1,8-dichloroanthracenes with substituents in position 10 and ortho-chloroaryne afford mixtures of 1,8,13- (syn) and 1,8,16-trichlorotriptycenes (anti). The syn/anti ratio is dependent on these substituents. Electropositive substituents like SiMe3 and GeMe3 lead to preferred formation of the syn-isomer, whereas CMe3 groups exclusively afford the anti-isomer. Different quantum chemical calculations including location of transition states give conflicting results, but indicate the importance of dispersion forces for an at least qualitative prediction of results. The syn-trichlorotriptycenes with SiMe3 and GeMe3 substituents were characterized by using NMR spectroscopy, mass spectrometry, and X-ray diffraction experiments. Triptycene represents one of a few rigid organic frameworks of D3h symmetry without any (Lewis-basic) heteroatoms. It was first synthesized by Bartlett et al. in 1942 using a multi-step procedure starting from anthracene and p-benzoquinone.[1] In 1956, Wittig and Ludwig reported a more efficient access to triptycene in one step from anthracene by reacting it with in situ-formed benzyne.[2] The symmetry and rigidity of triptycene have inspired a plethora of applications in fundamental and applied chemical research.[3-5] Substituted triptycenes are widely used, for example, as building blocks for fluorescent or non-fluorescent organic macromolecules, polymers, and liquid crystals,[3, 6] as rigid spacers in several Pd complexes used for cross coupling reactions,[7] as devices in molecular machines,[8] in crystal engineering processes,[9, 10] and as a basis for the design of highly porous organic materials with numerous applications.[11] Although the chemistry of triptycenes and their functionalization is generally in an advanced state, the 1,8,13-trisubstitution motif remains a challenge for synthesis. However, exactly this pattern is interesting to introduce three functionalities oriented in the same direction. We try to make use of such 1,8,13-trisubstituted triptycenes (also called syn-triptycenes) as rigid organic frameworks for constructing directed polydentate Lewis acids,[12, 13] but many other applications might be envisioned. syn-Triptycenes can be obtained through Diels–Alder reactions of 1,8-disubstituted anthracenes with ortho-functionalized arynes, a protocol introduced by Rogers and Averill in 1986.[14] The drawback of this method is that the corresponding anti-trisubstituted 1,8,16-isomer is always formed as the main product when, for example, Cl-functionalized anthracenes and arynes are used.[12, 14] In 2010, we reported attempts to increase the syn/anti ratio by making use of the steric interference of the (bulky) anthracene substituent at C-10 with the chlorine atom of the chloroaryne (Scheme 1). We expected this strategy to provide an increased formation of the syn-isomer. However, the steric influence of the C-10 substituent turned out to be minimal, whereas the electronic properties are dominant;[12] of all substituents tested, the biggest R=C(CH3)3 led to the formation of 100 % anti-isomer, despite the formation of an extremely deformed product by mutual repulsion of the Cl and R substituents, as indicated in Scheme 1 b.
Erscheinungsjahr
2018
Zeitschriftentitel
ChemistryOpen
Band
7
Ausgabe
1
Seite(n)
111-114
ISSN
2191-1363
Finanzierungs-Informationen
Open-Access-Publikationskosten wurden durch die Deutsche Forschungsgemeinschaft und die Universität Bielefeld gefördert.
Page URI
https://pub.uni-bielefeld.de/record/2917260

Zitieren

Lamm J-H, Vishnevskiy Y, Ziemann E, Neumann B, Stammler H-G, Mitzel NW. Regiochemical Control in Triptycene Formation-An Exercise in Subtle Balancing Multiple Factors. ChemistryOpen. 2018;7(1):111-114.
Lamm, J. - H., Vishnevskiy, Y., Ziemann, E., Neumann, B., Stammler, H. - G., & Mitzel, N. W. (2018). Regiochemical Control in Triptycene Formation-An Exercise in Subtle Balancing Multiple Factors. ChemistryOpen, 7(1), 111-114. doi:10.1002/open.201700196
Lamm, Jan-Hendrik, Vishnevskiy, Yury, Ziemann, Eric, Neumann, Beate, Stammler, Hans-Georg, and Mitzel, Norbert W. 2018. “Regiochemical Control in Triptycene Formation-An Exercise in Subtle Balancing Multiple Factors”. ChemistryOpen 7 (1): 111-114.
Lamm, J. - H., Vishnevskiy, Y., Ziemann, E., Neumann, B., Stammler, H. - G., and Mitzel, N. W. (2018). Regiochemical Control in Triptycene Formation-An Exercise in Subtle Balancing Multiple Factors. ChemistryOpen 7, 111-114.
Lamm, J.-H., et al., 2018. Regiochemical Control in Triptycene Formation-An Exercise in Subtle Balancing Multiple Factors. ChemistryOpen, 7(1), p 111-114.
J.-H. Lamm, et al., “Regiochemical Control in Triptycene Formation-An Exercise in Subtle Balancing Multiple Factors”, ChemistryOpen, vol. 7, 2018, pp. 111-114.
Lamm, J.-H., Vishnevskiy, Y., Ziemann, E., Neumann, B., Stammler, H.-G., Mitzel, N.W.: Regiochemical Control in Triptycene Formation-An Exercise in Subtle Balancing Multiple Factors. ChemistryOpen. 7, 111-114 (2018).
Lamm, Jan-Hendrik, Vishnevskiy, Yury, Ziemann, Eric, Neumann, Beate, Stammler, Hans-Georg, and Mitzel, Norbert W. “Regiochemical Control in Triptycene Formation-An Exercise in Subtle Balancing Multiple Factors”. ChemistryOpen 7.1 (2018): 111-114.
Alle Dateien verfügbar unter der/den folgenden Lizenz(en):
Creative Commons Namensnennung - Nicht kommerziell - Keine Bearbeitungen 4.0 International (CC BY-NC-ND 4.0):
Volltext(e)
Access Level
OA Open Access
Zuletzt Hochgeladen
2019-09-06T09:18:56Z
MD5 Prüfsumme
f86b775c448da45df5e9d16dbc3f53ef


Zitationen in Europe PMC

Daten bereitgestellt von Europe PubMed Central.

52 References

Daten bereitgestellt von Europe PubMed Central.


AUTHOR UNKNOWN, 1942

AUTHOR UNKNOWN, 1956
Iptycenes in the design of high performance polymers.
Swager TM., Acc. Chem. Res. 41(9), 2008
PMID: 18759462
Iptycenes in supramolecular and materials chemistry.
Chong JH, MacLachlan MJ., Chem Soc Rev 38(12), 2009
PMID: 20449050

AUTHOR UNKNOWN, 2011

AUTHOR UNKNOWN, 0

AUTHOR UNKNOWN, 2000
Synthesis of monodisperse oligo(1,4-phenyleneethynylene-alt-1,4-triptycyleneethynylene)s.
Maag D, Kottke T, Schulte M, Godt A., J. Org. Chem. 74(20), 2009
PMID: 19761236
Roof-shaped halide-bridged bimetallic complexes via ring expansion reaction.
Azerraf C, Cohen S, Gelman D., Inorg Chem 45(17), 2006
PMID: 16903761

AUTHOR UNKNOWN, 0
Molecular dials: hindered rotations in mono- and diferrocenyl anthracenes and triptycenes.
Nikitin K, Muller-Bunz H, Ortin Y, Muldoon J, McGlinchey MJ., J. Am. Chem. Soc. 132(49), 2010
PMID: 21090624
Molecular spur gears comprising triptycene rotators and bibenzimidazole-based stators.
Frantz DK, Linden A, Baldridge KK, Siegel JS., J. Am. Chem. Soc. 134(3), 2012
PMID: 22217296
Solid-state molecular folding and supramolecular structures of triptycene-derived secondary dicarboxamides.
Yang JS, Liu CP, Lin BC, Tu CW, Lee GH., J. Org. Chem. 67(21), 2002
PMID: 12375963

AUTHOR UNKNOWN, 0

AUTHOR UNKNOWN, 2011

AUTHOR UNKNOWN, 2012

AUTHOR UNKNOWN, 0

AUTHOR UNKNOWN, 2012

AUTHOR UNKNOWN, 2012

AUTHOR UNKNOWN, 2014

AUTHOR UNKNOWN, 2014

AUTHOR UNKNOWN, 2016

AUTHOR UNKNOWN, 0

AUTHOR UNKNOWN, 2010

AUTHOR UNKNOWN, 0

AUTHOR UNKNOWN, 0
Dialkylaluminium-, -gallium-, and -indium-based poly-Lewis acids with a 1,8-diethynylanthracene backbone.
Chmiel J, Neumann B, Stammler HG, Mitzel NW., Chemistry 16(39), 2010
PMID: 20827789

AUTHOR UNKNOWN, 2014

AUTHOR UNKNOWN, 2014
Polyalkynylanthracenes--syntheses, structures and their behaviour towards UV irradiation.
Lamm JH, Glatthor J, Weddeling JH, Mix A, Chmiel J, Neumann B, Stammler HG, Mitzel NW., Org. Biomol. Chem. 12(37), 2014
PMID: 25162922

AUTHOR UNKNOWN, 2017

AUTHOR UNKNOWN, 1986
The role of aryne distortions, steric effects, and charges in regioselectivities of aryne reactions.
Medina JM, Mackey JL, Garg NK, Houk KN., J. Am. Chem. Soc. 136(44), 2014
PMID: 25303232

AUTHOR UNKNOWN, 1980

AUTHOR UNKNOWN, 1990

AUTHOR UNKNOWN, 2014

AUTHOR UNKNOWN, 0

AUTHOR UNKNOWN, 1988

AUTHOR UNKNOWN, 2005

AUTHOR UNKNOWN, 0

AUTHOR UNKNOWN, 2013
Covalent radii revisited.
Cordero B, Gomez V, Platero-Prats AE, Reves M, Echeverria J, Cremades E, Barragan F, Alvarez S., Dalton Trans (21), 2008
PMID: 18478144

AUTHOR UNKNOWN, 0

AUTHOR UNKNOWN, 1994

AUTHOR UNKNOWN, 1996

AUTHOR UNKNOWN, 1996

AUTHOR UNKNOWN, 1934
Export

Markieren/ Markierung löschen
Markierte Publikationen

Open Data PUB

Web of Science

Dieser Datensatz im Web of Science®
Quellen

PMID: 29344439
PubMed | Europe PMC

Suchen in

Google Scholar