Communication
Arene-Free Ruthenium(II/IV)-Catalyzed Bifurcated Arylation for Oxidative C−H/C−H Functionalizations
Torben Rogge,
Prof. Dr. Lutz Ackermann,
Torben Rogge
Institut für Organische und Biomolekulare Chemie, Georg-August-Universität Göttingen, Tammannstraße 2, 37077 Göttingen, Germany
Search for more papers by this authorCorresponding Author
Prof. Dr. Lutz Ackermann
Institut für Organische und Biomolekulare Chemie, Georg-August-Universität Göttingen, Tammannstraße 2, 37077 Göttingen, Germany
Search for more papers by this authorTorben Rogge,
Prof. Dr. Lutz Ackermann,
Torben Rogge
Institut für Organische und Biomolekulare Chemie, Georg-August-Universität Göttingen, Tammannstraße 2, 37077 Göttingen, Germany
Search for more papers by this authorCorresponding Author
Prof. Dr. Lutz Ackermann
Institut für Organische und Biomolekulare Chemie, Georg-August-Universität Göttingen, Tammannstraße 2, 37077 Göttingen, Germany
Search for more papers by this authorGraphical Abstract
One way or the other: Experimental and computational studies provide insight into the selectivity-controlling factors in ruthenium-catalyzed C−H arylation and oxidative C−H/C−H functionalization.
Abstract
Experimental and computational studies provide detailed insight into the selectivity- and reactivity-controlling factors in bifurcated ruthenium-catalyzed direct C−H arylations and dehydrogenative C−H/C−H functionalizations. Thorough investigations revealed the importance of arene-ligand-free complexes for the formation of biscyclometalated intermediates within a ruthenium(II/IV/II) mechanistic manifold.
Supporting Information
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References
- 1For recent reviews, see:
- 1aS. M. Khake, N. Chatani, Trends Chem. 2019, 1, 524–539;
- 1bP. Gandeepan, T. Müller, D. Zell, G. Cera, S. Warratz, L. Ackermann, Chem. Rev. 2019, 119, 2192–2452;
- 1cP. H. Dixneuf, J. F. Soule, Chem. Rev. 2018, 118, 7532–7585;
- 1dP. Gandeepan, L. Ackermann, Chem 2018, 4, 199–222;
- 1eC. S. Wang, J. C. K. Chu, T. Rovis, Angew. Chem. Int. Ed. 2018, 57, 62–101; Angew. Chem. 2018, 130, 64–105;
- 1fK. Murakami, S. Yamada, T. Kaneda, K. Itami, Chem. Rev. 2017, 117, 9302–9332;
- 1gY. Park, Y. Kim, S. Chang, Chem. Rev. 2017, 117, 9247–9301;
- 1hJ. He, M. Wasa, K. S. L. Chan, Q. Shao, J.-Q. Yu, Chem. Rev. 2017, 117, 8754–8786;
- 1iJ. F. Hartwig, M. A. Larsen, ACS Cent. Sci. 2016, 2, 281–292;
- 1jL. McMurray, F. O'Hara, M. J. Gaunt, Chem. Soc. Rev. 2011, 40, 1885–1898, and references therein.
- 2
- 2aT. Cernak, K. D. Dykstra, S. Tyagarajan, P. Vachal, S. W. Krska, Chem. Soc. Rev. 2016, 45, 546–576;
- 2bM. Seki, Org. Process Res. Dev. 2016, 20, 867–877;
- 2cL. Ackermann, Org. Process Res. Dev. 2015, 19, 260–269.
- 3
- 3aT. Bura, J. T. Blaskovits, M. Leclerc, J. Am. Chem. Soc. 2016, 138, 10056–10071;
- 3bD. J. Schipper, K. Fagnou, Chem. Mater. 2011, 23, 1594–1600.
- 4J. Hubrich, T. Himmler, L. Rodefeld, L. Ackermann, ACS Catal. 2015, 5, 4089–4093.
- 5For selected reviews, see:
- 5aP. Nareddy, F. Jordan, M. Szostak, ACS Catal. 2017, 7, 5721–5745;
- 5bJ. A. Leitch, C. G. Frost, Chem. Soc. Rev. 2017, 46, 7145–7153;
- 5cC. Bruneau, P. H. Dixneuf, Top. Organomet. Chem. 2015, 55, 137–188;
- 5dC. Bruneau, Top. Organomet. Chem. 2014, 48, 195–236;
- 5eP. B. Arockiam, C. Bruneau, P. H. Dixneuf, Chem. Rev. 2012, 112, 5879–5918;
- 5fN. Chatani, S. Inoue, K. Yokota, H. Tatamidani, Y. Fukumoto, Pure Appl. Chem. 2010, 82, 1443–1451;
- 5gL. Ackermann, R. Vicente, Top. Curr. Chem. 2010, 292, 211–229;
- 5hL. Ackermann, R. Vicente, A. R. Kapdi, Angew. Chem. Int. Ed. 2009, 48, 9792–9826; Angew. Chem. 2009, 121, 9976–10011.
- 6On July 1, 2019, the prices of platinum, rhodium, iridium, palladium, and ruthenium were 837, 3350, 1480, 1549, and 253 US$ per troy oz, respectively. See: http://www.platinum.matthey.com/prices/price-charts.
- 7B. Li, P. H. Dixneuf, Chem. Soc. Rev. 2013, 42, 5744–5767.
- 8
- 8aS. Oi, E. Aizawa, Y. Ogino, Y. Inoue, J. Org. Chem. 2005, 70, 3113–3119;
- 8bS. Oi, S. Fukita, N. Hirata, N. Watanuki, S. Miyano, Y. Inoue, Org. Lett. 2001, 3, 2579–2581.
- 9
- 9aB. Li, C. Darcel, P. H. Dixneuf, ChemCatChem 2014, 6, 127–130;
- 9bB. Li, C. B. Bheeter, C. Darcel, P. Dixneuf, Top. Catal. 2014, 57, 833–842;
- 9cK. S. Singh, P. H. Dixneuf, ChemCatChem 2013, 5, 1313–1316;
- 9dE. Ferrer Flegeau, C. Bruneau, P. H. Dixneuf, A. Jutand, J. Am. Chem. Soc. 2011, 133, 10161–10170;
- 9eB. Li, C. B. Bheeter, C. Darcel, P. H. Dixneuf, ACS Catal. 2011, 1, 1221–1224;
- 9fP. B. Arockiam, C. Fischmeister, C. Bruneau, P. H. Dixneuf, Angew. Chem. Int. Ed. 2010, 49, 6629–6632; Angew. Chem. 2010, 122, 6779–6782;
- 9gI. Özdemir, S. Demir, B. Çetinkaya, C. Gourlaouen, F. Maseras, C. Bruneau, P. H. Dixneuf, J. Am. Chem. Soc. 2008, 130, 1156–1157.
- 10
- 10aS. R. Yetra, T. Rogge, S. Warratz, J. Struwe, W. Peng, P. Vana, L. Ackermann, Angew. Chem. Int. Ed. 2019, 58, 7490–7494; Angew. Chem. 2019, 131, 7569–7573;
- 10bR. Mei, C. Zhu, L. Ackermann, Chem. Commun. 2016, 52, 13171–13174;
- 10cL. Ackermann, A. V. Lygin, Org. Lett. 2011, 13, 3332–3335;
- 10dL. Ackermann, R. Vicente, H. K. Potukuchi, V. Pirovano, Org. Lett. 2010, 12, 5032–5035;
- 10eL. Ackermann, R. Born, P. Álvarez-Bercedo, Angew. Chem. Int. Ed. 2007, 46, 6364–6367; Angew. Chem. 2007, 119, 6482–6485;
- 10fL. Ackermann, A. Althammer, R. Born, Angew. Chem. Int. Ed. 2006, 45, 2619–2622; Angew. Chem. 2006, 118, 2681–2685;
- 10gL. Ackermann, Org. Lett. 2005, 7, 3123–3125.
- 11
- 11aY. Koseki, K. Kitazawa, M. Miyake, T. Kochi, F. Kakiuchi, J. Org. Chem. 2017, 82, 6503–6510;
- 11bC. J. Teskey, S. M. A. Sohel, D. L. Bunting, S. G. Modha, M. F. Greaney, Angew. Chem. Int. Ed. 2017, 56, 5263–5266; Angew. Chem. 2017, 129, 5347–5350;
- 11cA. Biafora, T. Krause, D. Hackenberger, F. Belitz, L. J. Gooßen, Angew. Chem. Int. Ed. 2016, 55, 14752–14755; Angew. Chem. 2016, 128, 14972–14975;
- 11dL. Huang, D. J. Weix, Org. Lett. 2016, 18, 5432–5435;
- 11eR. K. Chinnagolla, M. Jeganmohan, Chem. Commun. 2014, 50, 2442–2444;
- 11fY. Aihara, N. Chatani, Chem. Sci. 2013, 4, 664–670;
- 11gN. Dastbaravardeh, M. Schnürch, M. D. Mihovilovic, Org. Lett. 2012, 14, 1930–1933;
- 11hF. Kakiuchi, S. Kan, K. Igi, N. Chatani, S. Murai, J. Am. Chem. Soc. 2003, 125, 1698–1699.
- 12For a review, see:
- 12aC.-J. Li, Acc. Chem. Res. 2009, 42, 335–344; for selected examples, see:
- 12bS. Dana, D. Chowdhury, A. Mandal, F. A. S. Chipem, M. Baidya, ACS Catal. 2018, 8, 10173–10179;
- 12cD. Srimani, Y. Ben-David, D. Milstein, Angew. Chem. Int. Ed. 2013, 52, 4012–4015; Angew. Chem. 2013, 125, 4104–4107;
- 12dJ. Dong, Z. Long, F. Song, N. Wu, Q. Guo, J. Lan, J. You, Angew. Chem. Int. Ed. 2013, 52, 580–584; Angew. Chem. 2013, 125, 608–612;
- 12eX. Guo, G. Deng, C.-J. Li, Adv. Synth. Catal. 2009, 351, 2071–2074;
- 12fS. Oi, H. Sato, S. Sugawara, Y. Inoue, Org. Lett. 2008, 10, 1823–1826;
- 12gG. Deng, L. Zhao, C.-J. Li, Angew. Chem. Int. Ed. 2008, 47, 6278–6282; Angew. Chem. 2008, 120, 6374–6378.
- 13L. Ackermann, P. Novák, R. Vicente, V. Pirovano, H. K. Potukuchi, Synthesis 2010, 2245–2253.
- 14L. Ackermann, Acc. Chem. Res. 2014, 47, 281–295.
- 15
- 15aD. L. Davies, S. A. Macgregor, C. L. McMullin, Chem. Rev. 2017, 117, 8649–8709;
- 15bD. Balcells, E. Clot, O. Eisenstein, Chem. Rev. 2010, 110, 749–823.
- 16L. Ackermann, Chem. Rev. 2011, 111, 1315–1345.
- 17CCDC 1942734 contains the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre.
- 18
- 18aM. Simonetti, D. M. Cannas, X. Just-Baringo, I. J. Vitorica-Yrezabal, I. Larrosa, Nat. Chem. 2018, 10, 724–731;
- 18bJ. McIntyre, I. Mayoral-Soler, P. Salvador, A. Poater, D. J. Nelson, Catal. Sci. Technol. 2018, 8, 3174–3182;
- 18cM. Simonetti, G. J. Perry, X. C. Cambeiro, F. Julia-Hernandez, J. N. Arokianathar, I. Larrosa, J. Am. Chem. Soc. 2016, 138, 3596–3606;
- 18dP. Marcé, A. J. Paterson, M. F. Mahon, C. G. Frost, Catal. Sci. Technol. 2016, 6, 7068–7076;
- 18eH. H. Al Mamari, E. Diers, L. Ackermann, Chem. Eur. J. 2014, 20, 9739–9743;
- 18fL. Ackermann, A. Althammer, R. Born, Tetrahedron 2008, 64, 6115–6124;
- 18gL. Ackermann, A. Althammer, R. Born, Synlett 2007, 2833–2836.
- 19It is noteworthy that a complex kinetic behavior was observed when 2-bromobenzonitrile was employed as a reagent, indicating a distinct change in mechanism (Figure S9).
- 20For details, see the Supporting Information.
- 21
- 21aJ. Kim, K. Shin, S. Jin, D. Kim, S. Chang, J. Am. Chem. Soc. 2019, 141, 4137–4146;
- 21bS. Y. Hong, Y. Park, Y. Hwang, Y. B. Kim, M.-H. Baik, S. Chang, Science 2018, 359, 1016–1021;
- 21cK. Shin, Y. Park, M.-H. Baik, S. Chang, Nat. Chem. 2017, 10, 218–224.
- 22E. Zuidema, P. W. N. M. van Leeuwen, C. Bo, Organometallics 2005, 24, 3703–3710.
- 23
- 23aK. Naksomboon, J. Poater, F. M. Bickelhaupt, M. Á. Fernández-Ibáñez, J. Am. Chem. Soc. 2019, 141, 6719–6725;
- 23bD. Zell, M. Bursch, V. Müller, S. Grimme, L. Ackermann, Angew. Chem. Int. Ed. 2017, 56, 10378–10382; Angew. Chem. 2017, 129, 10514–10518;
- 23cW. Ma, R. Mei, G. Tenti, L. Ackermann, Chem. Eur. J. 2014, 20, 15248–15251.
- 24S. I. Gorelsky, D. Lapointe, K. Fagnou, J. Am. Chem. Soc. 2008, 130, 10848–10849.
