Stereoconvergent, Redox-Neutral Access to Tetrahydroquinoxalines through Relay Epoxide Opening/Amination of Alcohols
Guangda Xu
College of Chemistry, Liaoning University, Shenyang, 110036 P. R. China
These authors contributed equally to this work.
Search for more papers by this authorDr. Guoqiang Yang
Department of Chemistry, National University of Singapore, 3 Science Drive 3, 117543 Singapore, Singapore
These authors contributed equally to this work.
Search for more papers by this authorYue Wang
College of Chemistry, Liaoning University, Shenyang, 110036 P. R. China
Search for more papers by this authorDr. Pan-Lin Shao
Department of Chemistry, National University of Singapore, 3 Science Drive 3, 117543 Singapore, Singapore
Search for more papers by this authorJia Ning Nicolette Yau
Department of Chemistry, National University of Singapore, 3 Science Drive 3, 117543 Singapore, Singapore
Search for more papers by this authorBing Liu
College of Chemistry, Liaoning University, Shenyang, 110036 P. R. China
Search for more papers by this authorYunbo Zhao
College of Chemistry, Liaoning University, Shenyang, 110036 P. R. China
Search for more papers by this authorYe Sun
College of Chemistry, Liaoning University, Shenyang, 110036 P. R. China
Search for more papers by this authorXinxin Xie
College of Chemistry, Liaoning University, Shenyang, 110036 P. R. China
Search for more papers by this authorShuo Wang
College of Chemistry, Liaoning University, Shenyang, 110036 P. R. China
Search for more papers by this authorCorresponding Author
Prof. Yao Zhang
College of Chemistry, Liaoning University, Shenyang, 110036 P. R. China
Search for more papers by this authorCorresponding Author
Prof. Lixin Xia
College of Chemistry, Liaoning University, Shenyang, 110036 P. R. China
Search for more papers by this authorCorresponding Author
Prof. Yu Zhao
Department of Chemistry, National University of Singapore, 3 Science Drive 3, 117543 Singapore, Singapore
Search for more papers by this authorGuangda Xu
College of Chemistry, Liaoning University, Shenyang, 110036 P. R. China
These authors contributed equally to this work.
Search for more papers by this authorDr. Guoqiang Yang
Department of Chemistry, National University of Singapore, 3 Science Drive 3, 117543 Singapore, Singapore
These authors contributed equally to this work.
Search for more papers by this authorYue Wang
College of Chemistry, Liaoning University, Shenyang, 110036 P. R. China
Search for more papers by this authorDr. Pan-Lin Shao
Department of Chemistry, National University of Singapore, 3 Science Drive 3, 117543 Singapore, Singapore
Search for more papers by this authorJia Ning Nicolette Yau
Department of Chemistry, National University of Singapore, 3 Science Drive 3, 117543 Singapore, Singapore
Search for more papers by this authorBing Liu
College of Chemistry, Liaoning University, Shenyang, 110036 P. R. China
Search for more papers by this authorYunbo Zhao
College of Chemistry, Liaoning University, Shenyang, 110036 P. R. China
Search for more papers by this authorYe Sun
College of Chemistry, Liaoning University, Shenyang, 110036 P. R. China
Search for more papers by this authorXinxin Xie
College of Chemistry, Liaoning University, Shenyang, 110036 P. R. China
Search for more papers by this authorShuo Wang
College of Chemistry, Liaoning University, Shenyang, 110036 P. R. China
Search for more papers by this authorCorresponding Author
Prof. Yao Zhang
College of Chemistry, Liaoning University, Shenyang, 110036 P. R. China
Search for more papers by this authorCorresponding Author
Prof. Lixin Xia
College of Chemistry, Liaoning University, Shenyang, 110036 P. R. China
Search for more papers by this authorCorresponding Author
Prof. Yu Zhao
Department of Chemistry, National University of Singapore, 3 Science Drive 3, 117543 Singapore, Singapore
Search for more papers by this authorAbstract
We present an economical catalytic procedure to convert readily available 1,2-diaminobenzenes and terminal epoxides into valuable 1,2,3,4-tetrahydroquinoxalines in a highly enantioselective fashion. This procedure operates through relay zinc and iridium catalysis, and achieves redox-neutral and stereoconvergent production of valuable chiral heterocycles from racemic starting materials with water as the only side product. The use of commercially available reagents and catalysts and a convenient procedure also make this catalytic method attractive for practical application.
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References
- 1
- 1aM. H. S. A. Hamid, P. A. Slatford, J. M. J. Williams, Adv. Synth. Catal. 2007, 349, 1555–1575;
- 1bR. Yamaguchi, K.-i. Fujita, M. Zhu, Heterocycles 2010, 81, 1093–1140;
- 1cG. E. Dobereiner, R. H. Crabtree, Chem. Rev. 2010, 110, 681–703;
- 1dG. Guillena, D. J. Ramón, M. Yus, Chem. Rev. 2010, 110, 1611–1641;
- 1eA. J. Watson, J. M. J. Williams, Science 2010, 329, 635–636;
- 1fS. Bähn, S. Imm, L. Neubert, M. Zhang, H. Neumann, M. Beller, ChemCatChem 2011, 3, 1853–1864;
- 1gC. Gunanathan, D. Milstein, Science 2013, 341, 1229712;
- 1hS. Pan, T. Shibata, ACS Catal. 2013, 3, 704–712;
- 1iA. Quintard, J. Rodriguez, Chem. Commun. 2016, 52, 10456–10473;
- 1jF. Huang, Z. Liu, Z. Yu, Angew. Chem. Int. Ed. 2016, 55, 862–875; Angew. Chem. 2016, 128, 872–885;
- 1kA. Corma, J. Navas, M. J. Sabater, Chem. Rev. 2018, 118, 1410–1459;
- 1lT. Irrgang, R. Kempe, Chem. Rev. 2019, 119, 2524–2549.
- 2
- 2aR. Grigg, T. R. B. Mitchell, S. Sutthivaiyakit, N. Tongpenyai, Tetrahedron Lett. 1981, 22, 4107–4110;
- 2bR. Grigg, T. R. B. Mitchell, S. Sutthivaiyakit, N. Tongpenyai, J. Chem. Soc. Chem. Commun. 1981, 611–612;
- 2cY. Watanabe, Y. Tsuji, Y. Ohsugi, Tetrahedron Lett. 1981, 22, 2667–2670;
- 2dS.-I. Murahashi, K. Kondo, T. Hakata, Tetrahedron Lett. 1982, 23, 229–232.
- 3
- 3aO. Saidi, A. J. Blacker, G. W. Lamb, S. P. Marsden, J. E. Taylor, J. M. J. Williams, Org. Process Res. Dev. 2010, 14, 1046–1049;
- 3bM. A. Berliner, S. P. A. Duban, T. Makowski, K. N. B. Sitter, C. Wager, Y. Zhang, Org. Process Res. Dev. 2011, 15, 1052–1062;
- 3cJ. Leonard, A. J. Blacker, S. P. Marsden, M. F. Jones, K. R. Mulholland, R. Newton, Org. Process Res. Dev. 2015, 19, 1400–1410.
- 4Representative publications from our group:
- 4aY. Zhang, C. S. Lim, D. S. Sim, H.-J. Pan, Y. Zhao, Angew. Chem. Int. Ed. 2014, 53, 1399–1403; Angew. Chem. 2014, 126, 1423–1427;
- 4bZ.-Q. Rong, Y. Zhang, R. H. Chua, H.-J. Pan, Y. Zhao, J. Am. Chem. Soc. 2015, 137, 4944–4947;
- 4cL.-C. Yang, Y.-N. Wang, Y. Zhang, Y. Zhao, ACS Catal. 2017, 7, 93–97;
- 4dC. S. Lim, T. T. Quach, Y. Zhao, Angew. Chem. Int. Ed. 2017, 56, 7176–7180; Angew. Chem. 2017, 129, 7282–7286;
- 4eT.-L. Liu, T. W. Ng, Y. Zhao, J. Am. Chem. Soc. 2017, 139, 3643–3646;
- 4fR.-Z. Huang, K. K. Lau, Z. Li, T.-L. Liu, Y. Zhao, J. Am. Chem. Soc. 2018, 140, 14647–14654.
- 5Enantioselective aminations of secondary alcohols from other groups:
- 5aN. J. Oldenhuis, V. M. Dong, Z. Guan, J. Am. Chem. Soc. 2014, 136, 12548–12551;
- 5bF. G. Mutti, T. Knaus, N. S. Scrutton, M. Breuer, N. J. Turner, Science 2015, 349, 1525;
- 5cM. Peña-López, H. Neumann, M. Beller, Angew. Chem. Int. Ed. 2016, 55, 7826–7830; Angew. Chem. 2016, 128, 7957–7961;
- 5dP. Yang, C. Zhang, Y. Ma, C. Zhang, A. Li, B. Tang, J. S. Zhou, Angew. Chem. Int. Ed. 2017, 56, 14702–14706; Angew. Chem. 2017, 129, 14894–14898; Other enantioselective borrowing hydrogen transformations:
- 5eD. J. Shermer, P. A. Slatford, D. D. Edney, J. M. J. Williams, Tetrahedron: Asymmetry 2007, 18, 2845–2848;
- 5fA. Eka Putra, Y. Oe, T. Ohta, Eur. J. Org. Chem. 2013, 6146–6151;
- 5gA. Quintard, T. Constantieux, J. Rodriguez, Angew. Chem. Int. Ed. 2013, 52, 12883–12887; Angew. Chem. 2013, 125, 13121–13125;
- 5hJ. Zhang, J. Wang, Angew. Chem. Int. Ed. 2018, 57, 465–469; Angew. Chem. 2018, 130, 474–478;
- 5iD. Lichosyt, Y. Zhang, K. Hurej, P. Dydio, Nat. Catal. 2019, 2, 114–122.
- 6Related highly enantioselective catalytic C−C coupling involving transfer hydrogenation:
- 6aJ. M. Ketcham, I. Shin, T. P. Montgomery, M. J. Krische, Angew. Chem. Int. Ed. 2014, 53, 9142–9150; Angew. Chem. 2014, 126, 9294–9302;
- 6bK. D. Nguyen, B. Y. Park, T. Luong, H. Sato, V. J. Garza, M. J. Krische, Science 2016, 354, aah 5133;
- 6cM. Holmes, L. A. Schwartz, M. J. Krische, Chem. Rev. 2018, 118, 6026–6052.
- 7Examples of borrowing hydrogen reaction of structurally complex alcohol substrates:
- 7aK. Fujita, K. Yamamoto, R. Yamaguchi, Org. Lett. 2002, 4, 2691–2694;
- 7bC. T. Eary, D. Clausen, Tetrahedron Lett. 2006, 47, 6899–6902;
- 7cFor the use of diols as the substrate, see Ref. [5c].
- 8Selected reviews on bimetallic catalysis:
- 8aD. R. Pye, N. P. Mankad, Chem. Sci. 2017, 8, 1705–1718;
- 8b Dual Catalysis in Organic Synthesis (Ed.: ), Georg Thieme, Stuttgart, 2019.
- 9Selected examples of bimetallic enantioselective catalysis using Ir and Zn:
- 9aM. A. Schafroth, D. Sarlah, S. Krautwald, E. M. Carreira, J. Am. Chem. Soc. 2012, 134, 20276–20278;
- 9bO. F. Jeker, A. G. Kravina, E. M. Carreira, Angew. Chem. Int. Ed. 2013, 52, 12166–12169; Angew. Chem. 2013, 125, 12388–12391;
- 9cX. Huo, R. He, X. Zhang, W. Zhang, J. Am. Chem. Soc. 2016, 138, 11093–11096;
- 9dJ. Y. Hamilton, S. L. Rossler, E. M. Carreira, J. Am. Chem. Soc. 2017, 139, 8082–8085;
- 9eR. He, P. Liu, X. Huo, W. Zhang, Org. Lett. 2017, 19, 5513–5516;
- 9fY. Sempere, E. M. Carreira, Angew. Chem. Int. Ed. 2018, 57, 7654–7658; Angew. Chem. 2018, 130, 7780–7784.
- 10Selected examples:
- 10aM. Patel, R. J. McHugh, B. C. Cordova, R. M. Klabe, S. Erickson-Viitanen, G. L. Trainor, J. D. Rodgers, Bioorg. Med. Chem. Lett. 2000, 10, 1729–1731;
- 10bK. Torisu, et al., Bioorg. Med. Chem. 2004, 12, 5361–5378;
- 10cS. Li, X. Tian, D. M. Hartley, L. A. Feig, J. Neurosci. 2006, 26, 1721–1729;
- 10dM. Fantin, M. Marti, Y. P. Auberson, M. Morari, J. Neurochem. 2007, 103, 2200–2211;
- 10eC. T. Eary, et al., Bioorg. Med. Chem. Lett. 2007, 17, 2608–2613;
- 10fR. P. Law, et al., J. Med. Chem. 2018, 61, 4317–4334.
- 11Catalytic enantioselective synthesis of tetrahydroquinoxalines:
- 11aM. Massacret, P. Lhoste, D. Sinou, Eur. J. Org. Chem. 1999, 129–134;
10.1002/(SICI)1099-0690(199901)1999:1<129::AID-EJOC129>3.0.CO;2-6 CAS Web of Science® Google Scholar
- 11bJ.-L. Li, B. Han, K. Jiang, W. Du, Y.-C. Chen, Bioorg. Med. Chem. Lett. 2009, 19, 3952–3954;
- 11cO. Kanno, W. Kuriyama, Z. J. Wang, F. D. Toste, Angew. Chem. Int. Ed. 2011, 50, 9919–9122; Angew. Chem. 2011, 123, 10093–10096;
- 11dB. A. Hopkins, J. P. Wolfe, Chem. Sci. 2014, 5, 4840–4844.
- 12Examples of enantioseletive hydrogenation or transfer hydrogenation for the preparation of tetrahydroquinoxalines:
- 12aC. Bianchini, P. Barbaro, G. Scapacci, E. Farnetti, M. Graziani, Organometallics 1998, 17, 3308–3310;
- 12bN. Mršić, T. Jerphagnon, A. J. Minnaard, B. L. Feringa, J. G. de Vries, Adv. Synth. Catal. 2009, 351, 2549–2552;
- 12cW. Tang, L. Xu, Q.-H. Fan, J. Wang, B. Fan, Z. Zhou, K.-H. Lam, A. S. C. Chan, Angew. Chem. Int. Ed. 2009, 48, 9135–9138; Angew. Chem. 2009, 121, 9299–9302;
- 12dM. Rueping, F. Tato, F. R. Schoepke, Chem. Eur. J. 2010, 16, 2688–2691;
- 12eD.-W. Wang, D.-S. Wang, Q.-A. Chen, Y.-G. Zhou, Chem. Eur. J. 2010, 16, 1133–1136;
- 12fD. Cartigny, T. Nagano, T. Ayad, J. P. Genêt, T. Ohshima, K. Mashima, V. Ratovelomanana-Vidal, Adv. Synth. Catal. 2010, 352, 1886–1891;
- 12gS. Urban, N. Ortega, F. Glorius, Angew. Chem. Int. Ed. 2011, 50, 3803–3806; Angew. Chem. 2011, 123, 3887–3890;
- 12hQ.-A. Chen, D.-S. Wang, Y.-G. Zhou, Y. Duan, H.-J. Fan, Y. Yang, Z. Zhang, J. Am. Chem. Soc. 2011, 133, 6126–6129;
- 12iT. Nagano, A. Iimuro, R. Schwenk, T. Ohshima, Y. Kita, A. Togni, K. Mashima, Chem. Eur. J. 2012, 18, 11578–11592;
- 12jS. Fleischer, S. Zhou, S. Werkmeister, K. Junge, M. Beller, Chem. Eur. J. 2013, 19, 4997–5003;
- 12kF. Shi, W. Tan, H.-H. Zhang, M. Li, Q. Ye, G.-H. Ma, S.-J. Tu, G. Li, Adv. Synth. Catal. 2013, 355, 3715–3726;
- 12lN. Arai, Y. Saruwatari, K. Isobe, T. Ohkuma, Adv. Synth. Catal. 2013, 355, 2769–2774;
- 12mZ. Zhang, H. Du, Angew. Chem. Int. Ed. 2015, 54, 623–626; Angew. Chem. 2015, 127, 633–636;
- 12nY.-T. Xia, X.-T. Sun, L. Zhang, K. Luo, L. Wu, Chem. Eur. J. 2016, 22, 17151–17155.
- 13Precedents for non-stereoselective amination of diols using diamines:
- 13aL. L. R. Lorentz-Petersen, L. U. Nordstrøm, R. Madsen, Eur. J. Org. Chem. 2012, 6752–6759;
- 13bT. Yan, B. L. Feringa, K. Barta, Nat. Commun. 2014, 5, 5602;
- 13cK. O. Marichev, J. M. Takacs, ACS Catal. 2016, 6, 2205–2210.
- 14Cascade ring-opening/dehydrogenation reaction of anilines and epoxides:
- 14aT. Nishida, Y. Tokuda, M. Tsuchiya, J. Chem. Soc. Perkin Trans. 2 1995, 823–830;
- 14bC. S. Cho, J. H. Kim, H.-J. Choi, T.-J. Kim, S. C. Shim, Tetrahedron Lett. 2003, 44, 2975–2977;
- 14cM. Peña-López, H. Neumann, M. Beller, Chem. Eur. J. 2014, 20, 1818–1824.
- 15An excellent Minireview:
- 15aK. Natte, H. Neumann, M. Beller, R. V. Jagadeesh, Angew. Chem. Int. Ed. 2017, 56, 6384–6394; Angew. Chem. 2017, 129, 6482–6492; For selected recent examples, see:
- 15bT. T. Dang, B. Ramalingam, A. M. Seayad, ACS Catal. 2015, 5, 4082–4088;
- 15cV. N. Tsarev, Y. Morioka, J. Caner, Q. Wang, R. Ushimaru, A. Kudo, H. Naka, S. Saito, Org. Lett. 2015, 17, 2530–2533;
- 15dZ. Liu, Z. Yang, X. Yu, H. Zhang, B. Yu, Y. Zhao, Z. Liu, Adv. Synth. Catal. 2017, 359, 4278–4283;
- 15eR. Liang, S. Li, R. Wang, L. Lu, F. Li, Org. Lett. 2017, 19, 5790–5793;
- 15fG. Choi, S. H. Hong, Angew. Chem. Int. Ed. 2018, 57, 6166–6170; Angew. Chem. 2018, 130, 6274–6278;
- 15gL. Wang, H. Neumann, M. Beller, Angew. Chem. Int. Ed. 2019, 58, 5417–5421; Angew. Chem. 2019, 131, 5471–5475.
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