Enhanced Activity in the Tosylation of Tolanophanes via Supramolecular HgCl2 Recognition
Saeed Rastgar A , Hossein Reza Darabi
A B , Leila Sobhani A , Kioumars Aghapoor A , Rohoullah Firouzi A , Farshid Mohsenzadeh A , Hamed Yaghobi A and Farshad Jafary A
A Nano and Organic Synthesis Lab, Chemistry and Chemical Engineering Research Center of Iran, Pajoohesh Blvd, km 17, Karaj Highway, Tehran 14968-13151, Iran.
B Corresponding author. Email: darabi@ccerci.ac.ir
Australian Journal of Chemistry 73(7) 608-613 https://doi.org/10.1071/CH18376
Submitted: 4 August 2018 Accepted: 29 November 2019 Published: 24 January 2020
Abstract
The ‘self-activation’ of host molecules via the incorporation of a guest has received considerable attention in supramolecular catalysis. Here, we demonstrate how HgCl2 effects the tosylation rate of tolanophanes (1a–c: n = 2−4) with different alkyl chain lengths. Among these substrates, 1a has the highest strain in sp carbons and, therefore, is active even without assistance of HgCl2. In contrast, 1c is inert and needs to be activated in the presence of HgCl2. Therefore, the averaged reaction rate is in the following order: 1c > 1b > 1a, confirming the role of the supramolecular cavity of 1 over the strain of alkyne bonds. Ab initio calculations are consistent with the experimentally derived reactivity, supporting our size-fitting hypothesis. In contrast, acyclic analogues showed lower activity in the presence of HgCl2 to confirm the effect of the ring cavity. To gain more information, the HgCl2 complexation of 1b was examined by using 1H NMR and UV-vis spectroscopies. All products 5 are new and well characterized. The hydration of isomeric mixtures of 5b,c gave the corresponding single products 4b,c.
References
[1] F. Davis, S. Higson, Macrocycles: Construction, Chemistry and Nanotechnology Applications 2011 (Wiley: Chennai, India).[2] J. Brnjas-Kraljevi, G. Pifat-Mrzljak, Supramolecular Structure and Function 10 2011 (Springer: Dordrecht).
[3] H. Dodziuk, Introduction to Supramolecular Chemistry 2010 (Kluwer Academic: Warsaw).
[4] J. W. Steed, J. L. Atwood, Supramolecular Chemistry 2006 (Wiley: Chichester).
[5] K. Ariga, T. Kunitake, Supramolecular Chemistry: Fundamentals and Applications 2006 (Springer: Berlin).
[6] M. Raynal, P. Ballester, A. Vidal-Ferran, P. W. N. M. van Leeuwen, Chem. Soc. Rev. 2014, 43, 1660.
| Crossref | GoogleScholarGoogle Scholar | 24356298PubMed |
[7] L. A. Joyce, S. H. Shabbir, E. V. Anslyn, Chem. Soc. Rev. 2010, 39, 3621.
| Crossref | GoogleScholarGoogle Scholar | 20714470PubMed |
[8] M. L. Merlau, M. P. Mejia, S. T. Nguyen, J. T. Hupp, Angew. Chem. Int. Ed. 2001, 40, 4239.
| Crossref | GoogleScholarGoogle Scholar |
[9] A. Tsuda, C. Fukumoto, T. Oshima, J. Am. Chem. Soc. 2003, 125, 5811.
| Crossref | GoogleScholarGoogle Scholar | 12733922PubMed |
[10] A. Tsuda, T. Oshima, J. Org. Chem. 2002, 67, 1282.
| Crossref | GoogleScholarGoogle Scholar | 11846675PubMed |
[11] D. M. Bassani, V. Darcos, S. Mahony, J.-P. Desvergne, J. Am. Chem. Soc. 2000, 122, 8795.
| Crossref | GoogleScholarGoogle Scholar |
[12] M. Yoshizawa, Y. Takeyama, T. Kusukawa, M. Fujita, Angew. Chem. Int. Ed. 2002, 41, 1347.
| Crossref | GoogleScholarGoogle Scholar |
[13] G. T. Crisp, T. P. Bubner, Tetrahedron 1997, 53, 11881.
| Crossref | GoogleScholarGoogle Scholar |
[14] G. Brizius, U. H. F. Bunz, Org. Lett. 2002, 4, 2829.
| Crossref | GoogleScholarGoogle Scholar | 12182566PubMed |
[15] M. Mirza-Aghayan, H. R. Darabi, L. Ali-Saraie, M. Ghassemzadeh, M. Bolourtchian, M. Jalali-Heravi, B. Neumüller, Z. Anorg. Allg. Chem 2002, 628, 681.
| Crossref | GoogleScholarGoogle Scholar |
[16] H. R. Darabi, M. Mirza-Aghayan, L. Ali-Saraie, M. Bolourtchian, B. Neumueller, M. Ghassemzadeh, Supramol. Chem. 2003, 15, 55.
| Crossref | GoogleScholarGoogle Scholar |
[17] H. R. Darabi, A. R. Mohebbi, M. Bolourtchian, Supramol. Chem. 2003, 15, 465.
| Crossref | GoogleScholarGoogle Scholar |
[18] R. Shukla, D. M. Brody, S. V. Lindeman, R. Rathore, J. Org. Chem. 2006, 71, 6124.
| Crossref | GoogleScholarGoogle Scholar | 16872195PubMed |
[19] R. Shukla, S. V. Lindeman, R. Rathore, Org. Lett. 2007, 9, 1291.
| Crossref | GoogleScholarGoogle Scholar | 17326648PubMed |
[20] H. R. Darabi, K. Jadidi, A. R. Mohebbi, L. Faraji, K. Aghapoor, S. Shahbazian, M. Azimzadeh Arani, S. M. Nasseri, Supramol. Chem. 2008, 20, 327.
| Crossref | GoogleScholarGoogle Scholar |
[21] H. R. Darabi, M. Azimzadeh Arani, M. Tafazzoli, M. Ghiasi, Monatsh. Chem. 2008, 139, 1185.
| Crossref | GoogleScholarGoogle Scholar |
[22] H. R. Darabi, M. Azimzadeh Arani, A. Motamedi, R. Firouzi, R. Herges, A. R. Mohebbi, S. Nasseri, C. Naether, Supramol. Chem. 2009, 21, 632.
| Crossref | GoogleScholarGoogle Scholar |
[23] H. R. Darabi, A. Darestani Farahani, M. Hashemi Karouei, K. Aghapoor, R. Firouzi, R. Herges, A. R. Mohebbi, C. Naether, Supramol. Chem. 2012, 24, 653.
| Crossref | GoogleScholarGoogle Scholar |
[24] H. R. Darabi, S. Rastgar, K. Aghapoor, F. Mohsenzadeh, Monatsh. Chem. 2018, 149, 1121.
| Crossref | GoogleScholarGoogle Scholar |
[25] H. R. Darabi, M. Mirzakhani, K. Aghapoor, K. Jadidi, L. Faraji, N. Sakhaee, J. Organomet. Chem. 2013, 740, 131.
| Crossref | GoogleScholarGoogle Scholar |
[26] H. R. Darabi, M. Mirzakhani, K. Aghapoor, J. Organomet. Chem. 2015, 786, 10.
| Crossref | GoogleScholarGoogle Scholar |
[27] H. R. Darabi, S. Rastgar, E. Khatamifar, K. Aghapoor, H. Sayahi, R. Firouzi, Appl. Organomet. Chem. 2017, 31, e3812.
| Crossref | GoogleScholarGoogle Scholar |
[28] H. Liu, Y. Wei, C. Cai, Synlett 2016, 27, 2378.
| Crossref | GoogleScholarGoogle Scholar |
