Cavitands as Containers for α,ω-Dienes and Chaperones for Olefin Metathesis
Dr. Nai-Wei Wu
Center for Supramolecular and Catalytic Chemistry and Department of Chemistry, Shanghai University, 99 Shang-Da Road, Shanghai, 200444 China
Search for more papers by this authorDr. Ioannis D. Petsalakis
Theoretical and Physical Chemistry Institute, National Hellenic Research Foundation, 48 Vassileos Constantinou Ave., Athens, 116 35 Greece
Search for more papers by this authorDr. Giannoula Theodorakopoulos
Theoretical and Physical Chemistry Institute, National Hellenic Research Foundation, 48 Vassileos Constantinou Ave., Athens, 116 35 Greece
Search for more papers by this authorCorresponding Author
Prof. Dr. Yang Yu
Center for Supramolecular and Catalytic Chemistry and Department of Chemistry, Shanghai University, 99 Shang-Da Road, Shanghai, 200444 China
Search for more papers by this authorCorresponding Author
Prof. Dr. Julius Rebek Jr.
Center for Supramolecular and Catalytic Chemistry and Department of Chemistry, Shanghai University, 99 Shang-Da Road, Shanghai, 200444 China
The Skaggs Institute for Chemical Biology and Department of Chemistry, The Scripps Research Institute, 10550 North Torrey Pines Road, La Jolla, California, 92037 USA
Search for more papers by this authorDr. Nai-Wei Wu
Center for Supramolecular and Catalytic Chemistry and Department of Chemistry, Shanghai University, 99 Shang-Da Road, Shanghai, 200444 China
Search for more papers by this authorDr. Ioannis D. Petsalakis
Theoretical and Physical Chemistry Institute, National Hellenic Research Foundation, 48 Vassileos Constantinou Ave., Athens, 116 35 Greece
Search for more papers by this authorDr. Giannoula Theodorakopoulos
Theoretical and Physical Chemistry Institute, National Hellenic Research Foundation, 48 Vassileos Constantinou Ave., Athens, 116 35 Greece
Search for more papers by this authorCorresponding Author
Prof. Dr. Yang Yu
Center for Supramolecular and Catalytic Chemistry and Department of Chemistry, Shanghai University, 99 Shang-Da Road, Shanghai, 200444 China
Search for more papers by this authorCorresponding Author
Prof. Dr. Julius Rebek Jr.
Center for Supramolecular and Catalytic Chemistry and Department of Chemistry, Shanghai University, 99 Shang-Da Road, Shanghai, 200444 China
The Skaggs Institute for Chemical Biology and Department of Chemistry, The Scripps Research Institute, 10550 North Torrey Pines Road, La Jolla, California, 92037 USA
Search for more papers by this authorAbstract
Described herein is the behavior of α,ω-dienes sequestered within cavitands in aqueous (D2O) solution. Hydrophobic forces drive the dienes into the cavitands in conformations that best fill the available space. Shorter dienes (C9 and C10) bind in compressed conformations that tumble rapidly in the cavitands. Longer dienes induce capsule formation between cavitands with self-complementary hydrogen bonding sites, where the dienes exist in extended conformations. In cavitands unable to form capsules, longer dienes adopt folded structures. The wider open ends allow the synthesis of medium-sized cycloalkenes by ring-closing metathesis reactions with the Hoveyda–Grubbs-II catalyst. Yields of cycloheptene and cyclooctene were enhanced by the chaperones in water when compared with reactions of the free dienes in either aqueous media or chloroform, and even cyclononene could be prepared within the cavitand.
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References
- 1
- 1aC. M. Hong, D. M. Kaphan, R. G. Bergman, K. N. Raymond, F. D. Toste, J. Am. Chem. Soc. 2017, 139, 8013–8021;
- 1bB. M. Schmidt, T. Osuga, T. Sawada, M. Hoshino, M. Fujita, Angew. Chem. Int. Ed. 2016, 55, 1561–1564; Angew. Chem. 2016, 128, 1587–1590;
- 1cW. M. Hart-Cooper, C. Zhao, R. M. Triano, P. Yaghoubi, H. L. Ozores, K. N. Burford, F. D. Toste, R. G. Bergman, K. N. Raymond, Chem. Sci. 2015, 6, 1383–1393;
- 1dC. J. Hastings, M. P. Backlund, R. G. Bergman, K. N. Raymond, Angew. Chem. Int. Ed. 2011, 50, 10570–10573; Angew. Chem. 2011, 123, 10758–10761;
- 1eM. Fujita, M. Tominaga, A. Hori, B. Therrien, Acc. Chem. Res. 2005, 38, 369–378;
- 1fD. Fiedler, R. G. Bergman, K. N. Raymond, Angew. Chem. Int. Ed. 2004, 43, 6748–6751; Angew. Chem. 2004, 116, 6916–6919;
- 1gJ. Murray, K. Kim, T. Ogoshi, W. Yao, B. C. Gibb, Chem. Soc. Rev. 2017, 46, 2479–2496;
- 1hA. K. Sundaresan, V. Ramamurthy, Org. Lett. 2007, 9, 3575–3578;
- 1iP. Jagadesan, B. Mondal, A. Parthasarathy, V. J. Rao, V. Ramamurthy, Org. Lett. 2013, 15, 1326–1329;
- 1jA. K. Sundaresan, V. Ramamurthy, Photochem. Photobiol. Sci. 2008, 7, 1555–1564;
- 1kL. Catti, Q. Zhang, K. Tiefenbacher, Chem. Eur. J. 2016, 22, 9060–9066;
- 1lQ. Zhang, K. Tiefenbacher, Nat. Chem. 2015, 7, 197–202;
- 1mJ. Rebek, Jr., Acc. Chem. Res. 2009, 42, 1660–1668;
- 1nD. Ajami, J. Rebek, Jr., Acc. Chem. Res. 2013, 46, 990–999.
- 2S. Mosca, Y. Yu, J. V. Gavette, K.-D. Zhang, J. Rebek, Jr., J. Am. Chem. Soc. 2015, 137, 14582–14585.
- 3M. H. K. Ebbing, M. J. Villa, J. M. Valpuesta, P. Prados, J. de Mendoza, Proc. Natl. Acad. Sci. USA 2002, 99, 4962–4966.
- 4K.-D. Zhang, D. Ajami, J. Rebek, Jr., J. Am. Chem. Soc. 2013, 135, 18064–18066.
- 5D. J. Cram, H.-J. Choi, J. A. Bryant, C. B. Knobler, J. Am. Chem. Soc. 1992, 114, 7748–7765.
- 6
- 6aZ. Lin, J. Sun, B. Efremovska, R. Warmuth, Chem. Eur. J. 2012, 18, 12864–12872;
- 6bT. Chavagnan, C. Bauder, D. Sémeril, D. Matt, L. Toupet, Eur. J. Org. Chem. 2017, 70–76;
- 6cK. Wang, B. C. Gibb, J. Org. Chem. 2017, 82, 4279–4288.
- 7
- 7aS. Mosca, D. Ajami, J. Rebek, Jr., Proc. Natl. Acad. Sci. USA 2015, 112, 11181–11186;
- 7bY. Yu, S. Mosca, J. Rebek, Jr., Heterocycles. 2017, 95, 127–130.
- 8Y. Wang, X. Dong, R. C. Larock, J. Org. Chem. 2003, 68, 3090–3098.
- 9J. V. Gavette, K.-D. Zhang, D. Ajami, J. Rebek, Jr., Org. Biomol. Chem. 2014, 12, 6561–6563.
- 10
- 10aJ. H. Jordan, B. C. Gibb, Chem. Soc. Rev. 2015, 44, 547–585;
- 10bL. Trembleau, J. Rebek, Jr., Science 2003, 301, 1219–1220.
- 11K.-D. Zhang, D. Ajami, J. V. Gavette, J. Rebek, Jr., Chem. Commun. 2014, 50, 4895–4897.
- 12
- 12aQ. Shi, M. P. Mower, D. G. Blackmond, J. Rebek, Jr., Proc. Natl. Acad. Sci. USA 2016, 113, 9199–9203;
- 12bY. Yu, K.-D. Zhang, I. D. Petsalakis, G. Theodorakopoulos, J. Rebek, Jr., Supramol. Chem. 2018, 30, 473–478.
- 13Gaussian 16, Revision B.01, M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, G. Scalmani, V. Barone, G. A. Petersson, H. Nakatsuji, X. Li, M. Caricato, A. V. Marenich, J. Bloino, B. G. Janesko, R. Gomperts, B. Mennucci, H. P. Hratchian, J. V. Ortiz, A. F. Izmaylov, J. L. Sonnenberg, D. Williams-Young, F. Ding, F. Lipparini, F. Egidi, J. Goings, B. Peng, A. Petrone, T. Henderson, D. Ranasinghe, V. G. Zakrzewski, J. Gao, N. Rega, G. Zheng, W. Liang, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, T. Vreven, K. Throssell, J. A. Montgomery, Jr., J. E. Peralta, F. Ogliaro, M. J. Bearpark, J. J. Heyd, E. N. Brothers, K. N. Kudin, V. N. Staroverov, T. A. Keith, R. Kobayashi, J. Normand, K. Raghavachari, A. P. Rendell, J. C. Burant, S. S. Iyengar, J. Tomasi, M. Cossi, J. M. Millam, M. Klene, C. Adamo, R. Cammi, J. W. Ochterski, R. L. Martin, K. Morokuma, O. Farkas, J. B. Foresman, and D. J. Fox, Gaussian, Inc., Wallingford CT, 2016.
- 14
- 14aQ. Shi, D. Masseroni, J. Rebek, Jr., J. Am. Chem. Soc. 2016, 138, 10846–10848;
- 14bD. Masseroni, S. Mosca, M. P. Mower, D. G. Blackmond, J. Rebek, Jr., Angew. Chem. Int. Ed. 2016, 55, 8290–8293; Angew. Chem. 2016, 128, 8430–8433;
- 14cN.-W. Wu, J. Rebek, Jr., J. Am. Chem. Soc. 2016, 138, 7512–7515.
- 15For selected reviews, see:
- 15aK. C. Nicolaou, P. G. Bulger, D. Sarlah, Angew. Chem. Int. Ed. 2005, 44, 4490–4527; Angew. Chem. 2005, 117, 4564–4601;
- 15bR. R. Schrock, Angew. Chem. Int. Ed. 2006, 45, 3748–3759; Angew. Chem. 2006, 118, 3832–3844;
- 15cG. C. Vougioukalakis, R. H. Grubbs, Chem. Rev. 2010, 110, 1746–1787.
- 16
- 16aT. S. Ahmed, R. H. Grubb, Angew. Chem. Int. Ed. 2017, 56, 11213–11216; Angew. Chem. 2017, 129, 11365–11368;
- 16bD. J. Nelson, I. W. Ashworth, I. H. Hillier, S. H. Kyne, S. Pandian, J. A. Parkinson, J. M. Percy, G. Rinaudo, M. A. Vincent, Chem. Eur. J. 2011, 17, 13087–13094;
- 16cA. Fürstner, O. R. Thiel, C. W. Lehmann, Organometallics 2002, 21, 331–335.
- 17
- 17aA. H. Hoveyda, A. R. Zhugralin, Nature 2007, 450, 243–251;
- 17bJ. B. Binder, J. J. Blank, R. T. Raines, Org. Lett. 2007, 9, 4885–4888.
- 18
- 18aL. Mitchell, J. A. Parkinson, J. M. Percy, K. Singh, J. Org. Chem. 2008, 73, 2389–2395;
- 18bS. J. Miller, S.-H. Kim, Z.-R. Chen, R. H. Grubbs, J. Am. Chem. Soc. 1995, 117, 2108–2109.
- 19
- 19aM. T. Crimmins, A. L. Choy, J. Org. Chem. 1997, 62, 7548–7549;
- 19bM. T. Crimmins, E. A. Tabet, J. Am. Chem. Soc. 2000, 122, 5473–5476.
- 20H. E. Maier, Angew. Chem. Int. Ed. 2000, 39, 2073–2077;
10.1002/1521-3773(20000616)39:12<2073::AID-ANIE2073>3.0.CO;2-0 CAS PubMed Web of Science® Google ScholarAngew. Chem. 2000, 112, 2153–2157.
- 21M. Arisawa, Y. Terada, M. Nakagawa, A. Nishida, Angew. Chem. Int. Ed. 2002, 41, 4732–4734; Angew. Chem. 2002, 114, 4926–4928.
- 22A. Sytniczuk, M. Dąbrowski, Ł. Banach, M. Urban, S. Czarnocka-Śniadała, M. Milewski, A. Kajetanowicz, K. Grela, J. Am. Chem. Soc. 2018, 140, 8895–8901.
- 23T. Brendgen, T. Fahlbusch, M. Frank, D. T. Schühle, M. Seßler, J. Schatz, Adv. Synth. Catal. 2009, 351, 303–307.
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