Proving Triptycene Homoconjugation with the Same Chromophore but Different Connectivity to the Core

Sven M. Elbert; Tobias Kirschbaum; Frank Rominger; Michael Mastalerz

doi:10.1055/s-0041-1726304

Organic Materials, Table of Contents

CC BY-NC-ND 4.0 · Organic Materials 2021; 03(02): 097-102
DOI: 10.1055/s-0041-1726304

Focus Issue: Peter Bäuerle 65th Birthday

Short Communication

Proving Triptycene Homoconjugation with the Same Chromophore but Different Connectivity to the Core

Sven M. Elbert

^aOrganisch-Chemisches Institut, Ruprecht-Karls-Universität Heidelberg, Im Neuenheimer Feld 270, 69120 Heidelberg, Germany

,

Tobias Kirschbaum

^aOrganisch-Chemisches Institut, Ruprecht-Karls-Universität Heidelberg, Im Neuenheimer Feld 270, 69120 Heidelberg, Germany

,

Frank Rominger

^aOrganisch-Chemisches Institut, Ruprecht-Karls-Universität Heidelberg, Im Neuenheimer Feld 270, 69120 Heidelberg, Germany

,

Michael Mastalerz

^aOrganisch-Chemisches Institut, Ruprecht-Karls-Universität Heidelberg, Im Neuenheimer Feld 270, 69120 Heidelberg, Germany

› Author Affiliations

Abstract

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Abstract

Homoconjugation is a phenomenon discussed for various π-systems where classical conjugation is broken by e.g. methylene units but still a stabilization by electronic communication exists. In this respect, triptycene with its rigid C₃ symmetric geometry is an ideal scaffold to study this phenomenon. Although several studies based on triptycene strengthen the hypothesis of homoconjugation, in all described cases the electronic communication through space relies on different π-blades. Here, two triptycenes are presented having the exact same π-extended chromophore, but differently annulated to the bicyclic core. Both compounds were investigated by spectroscopic as well as computational means and compared with the corresponding model compound, elucidating the influence of the attachment site to the triptycene core on potential homoconjugation.

Key words

triptycenes - homoconjugation - Pictet–Spengler reaction - three-dimensional π-extended molecules

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References

References And Notes
1 Harada N, Tamai Y, Uda H. J. Am. Chem. Soc. 1980; 102: 506

2a Martin H.-D, Mayer B. Angew. Chem. Int. Ed. Engl. 1983; 22: 283
2b Murata I. Pure Appl. Chem. 1983; 55: 323
2c Ohno K, Ishida T, Naitoh Y, Izumi Y. J. Am. Chem. Soc. 1985; 107: 8082

3a Yamamura K, Nakasuji K, Murata I, Inagaki S. J. Chem. Soc. Chem. Comm. 1982; 396
3b Harada N, Uda H, Nakasuji K, Murata I. J. Chem. Soc., Perkin Trans. 2 1989; 1449

4 Kawasumi K, Wu T, Zhu T, Chae HS, Van Voorhis T, Baldo MA, Swager TM. J. Am. Chem. Soc. 2015; 137: 11908
5 Bartlett PD, Lewis ES. J. Am. Chem. Soc. 1950; 72: 1005
6 Martin H.-D, Mayer B, Gleiter R, Schäfer W, Vögtle F. Chem. Ber. 1983; 116: 2546
7 Talipov MR, Navale TS, Rathore R. Angew. Chem. Int. Ed. 2015; 54: 14468

8a Klanderman BH, Perkins WC. J. Org. Chem. 1969; 34: 630
8b Rees JH. J. Chem. Soc., Perkin Trans. 2 1975; 945

9 Chong JH, MacLachlan MJ. Inorg. Chem. 2006; 45: 1442
10 Li P.-F, Chen C.-F. J. Org. Chem. 2012; 77: 9250
11 Baumgärtner K, Hoffmann M, Rominger F, Elbert SM, Dreuw A, Mastalerz M. J. Org. Chem. 2020; 85: 15256

12a Harada N, Tamai Y, Takuma Y, Uda H. J. Am. Chem. Soc. 1980; 102: 501
12b Doerner T, Gleiter R, Neugebauer FA. Eur. J. Org. Chem. 1998; 1615

13 Elbert SM, Wagner P, Kanagasundaram T, Rominger F, Mastalerz M. Chem. Eur. J. 2017; 23: 935

14a Zhang C, Chen C.-F. J. Org. Chem. 2006; 71: 6626
14b Menke EH, Lami V, Vaynzof Y, Mastalerz M. Chem. Commun. 2016; 52: 1048

15a Skvarchenko VR, Shalaev VK, Klabunovskii EI. Russ. Chem. Rev. 1974; 43: 951
15b Shalaev VK, Getmanova EV, Skvarchenko VR. Vestnik Moskov Univ. 1973; 14: 740

16 Shalaev VK, Getmanova EV, Skvarchenko VR. Zh. Org. Khim. 1976; 12: 191
17 Yang X, Rominger F, Mastalerz M. Org. Lett. 2018; 20: 7270
18 Netherton MR, Fu GC. Org. Lett. 2001; 3: 4295

19a Elbert SM, Reinschmidt M, Baumgartner K, Rominger F, Mastalerz M. Eur. J. Org. Chem. 2018; 532
19b Elbert SM, Rominger F, Mastalerz M. Z. Anorg. Allg. Chem. 2018; 644: 606

20 The structural isomerism is only referred to the chromophoric units and the central triptycene. The tert-butyl units of 11 are to be neglected in this respect, yet had to be introduced due to solubility reasons
21 Elbert SM, Rominger F, Mastalerz M. Chem. Eur. J. 2014; 20: 16707
22 Coggeshall ND, Glessner AS. J. Am. Chem. Soc. 1949; 71: 3150
23 Grimme S, Ehrlich S, Goerigk L. J. Comput. Chem. 2011; 32: 1456
24 Ueberricke L, Benke BP, Kirschbaum T, Hahn S, Rominger F, Bunz UH. F, Mastalerz M. Chem. Eur. J. 2021; 27: 2043

Supplementary Material

Supporting Information