Aminoazanium of DABCO: An Amination Reagent for Alkyl and Aryl Pinacol Boronates
Xingxing Liu
College of Chemical Engineering, Zhejiang University of Technology, Hangzhou, 310014 P. R. China
State Key Laboratory for Oxo Synthesis and Selective Oxidation, Suzhou Research Institute, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou, 730000 P. R. China
These authors contributed equally to this work.
Search for more papers by this authorQing Zhu
State Key Laboratory for Oxo Synthesis and Selective Oxidation, Suzhou Research Institute, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou, 730000 P. R. China
University of Chinese Academy of Sciences, Beijing, 100049 P. R. China
These authors contributed equally to this work.
Search for more papers by this authorDu Chen
State Key Laboratory for Oxo Synthesis and Selective Oxidation, Suzhou Research Institute, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou, 730000 P. R. China
University of Chinese Academy of Sciences, Beijing, 100049 P. R. China
Search for more papers by this authorProf. Lu Wang
State Key Laboratory for Oxo Synthesis and Selective Oxidation, Suzhou Research Institute, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou, 730000 P. R. China
Search for more papers by this authorCorresponding Author
Prof. Liqun Jin
College of Chemical Engineering, Zhejiang University of Technology, Hangzhou, 310014 P. R. China
Search for more papers by this authorCorresponding Author
Prof. Chao Liu
State Key Laboratory for Oxo Synthesis and Selective Oxidation, Suzhou Research Institute, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou, 730000 P. R. China
Key Laboratory of Organosilicon Chemistry and Material Technology of Ministry of Education, Hangzhou Normal University, Hangzhou, 311121 P. R. China
Search for more papers by this authorXingxing Liu
College of Chemical Engineering, Zhejiang University of Technology, Hangzhou, 310014 P. R. China
State Key Laboratory for Oxo Synthesis and Selective Oxidation, Suzhou Research Institute, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou, 730000 P. R. China
These authors contributed equally to this work.
Search for more papers by this authorQing Zhu
State Key Laboratory for Oxo Synthesis and Selective Oxidation, Suzhou Research Institute, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou, 730000 P. R. China
University of Chinese Academy of Sciences, Beijing, 100049 P. R. China
These authors contributed equally to this work.
Search for more papers by this authorDu Chen
State Key Laboratory for Oxo Synthesis and Selective Oxidation, Suzhou Research Institute, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou, 730000 P. R. China
University of Chinese Academy of Sciences, Beijing, 100049 P. R. China
Search for more papers by this authorProf. Lu Wang
State Key Laboratory for Oxo Synthesis and Selective Oxidation, Suzhou Research Institute, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou, 730000 P. R. China
Search for more papers by this authorCorresponding Author
Prof. Liqun Jin
College of Chemical Engineering, Zhejiang University of Technology, Hangzhou, 310014 P. R. China
Search for more papers by this authorCorresponding Author
Prof. Chao Liu
State Key Laboratory for Oxo Synthesis and Selective Oxidation, Suzhou Research Institute, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou, 730000 P. R. China
Key Laboratory of Organosilicon Chemistry and Material Technology of Ministry of Education, Hangzhou Normal University, Hangzhou, 311121 P. R. China
Search for more papers by this authorAbstract
The aminoazanium of DABCO (H2N-DABCO) has been developed as a general and practical amination reagent for the direct amination of alkyl and aryl pinacol boronates. This compound is stable and practical for use as a reagent. Various primary, secondary. and tertiary alkyl−Bpin and aryl−Bpin substrates were aminated to give the corresponding amine derivatives. The amination is stereospecific. The anti-Markovnikov hydroamination of olefins was easily achieved by catalytic hydroboration with HBpin and in subsequent situ amination using H2N-DABCO. Moreover, the combination of 1,2-diboration of olefins, using B2pin2, with this amination process achieved the unprecedented 1,2-diamination of olefins. The amination protocol was also successfully extended to aryl pinacol boronates.
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References
- 1
- 1aD. G. Hall, Boronic Acids: Preparation and Applications in Organic Synthesis Medicine and Materials, Vol. 1 and 2, 2nd ed., Wiley-VCH, Weinheim, 2011;
- 1bR. S. Dhillon, Hydroboration and Organic Synthesis, Springer, Heidelberg, 2007.
- 2
- 2aH. C. Brown, W. R. Heydkamp, E. Breuer, W. S. Murphy, J. Am. Chem. Soc. 1964, 86, 3565–3566;
- 2bA. G. Davies, S. C. W. Hook, B. P. Roberts, J. Organomet. Chem. 1970, 23, C 11–C13;
- 2cH. C. Brown, A. Suzui, S. Sonao, M. Itoh, M. M. Midland, J. Am. Chem. Soc. 1971, 93, 4329–4330;
- 2dH. C. Brown, M. M. Midland, A. B. Levy, J. Am. Chem. Soc. 1973, 95, 2394–2396;
- 2eY. Tamura, J. Minamikawa, S. Fujii, M. Ikeda, Synthesis 1974, 196–196;
- 2fG. W. Kabalka, D. A. Henderson, R. S. Varma, Organometallics 1987, 6, 1369–1370;
- 2gH. C. Brown, A. M. Salunkhe, B. Singaram, J. Org. Chem. 1991, 56, 1170–1175;
- 2hO. I. Phanstiel, Q. X. Wang, D. H. Powell, M. P. Ospina, B. A. Leeson, J. Org. Chem. 1999, 64, 803–806.
- 3
- 3aL. Ou, J. Shao, G. Zhang, Y. Yu, Tetrahedron Lett. 2011, 52, 1430–1431;
- 3bC. Zhu, G. Li, D. H. Ess, J. R. Falck, L. Kurti, J. Am. Chem. Soc. 2012, 134, 18253–18256;
- 3cV. Coeffard, X. Moreau, C. Thomassigny, C. Greck, Angew. Chem. Int. Ed. 2013, 52, 5684–5686; Angew. Chem. 2013, 125, 5794–5796;
- 3dN. Chatterjee, A. Goswami, Org. Biomol. Chem. 2015, 13, 7940–7945;
- 3eS. Voth, J. W. Hollett, J. A. McCubbin, J. Org. Chem. 2015, 80, 2545–2553;
- 3fN. Chatterjee, M. Arfeen, P. V. Bharatam, A. Goswami, J. Org. Chem. 2016, 81, 5120–5127;
- 3gS. Roscales, A. G. Csaky, Org. Lett. 2018, 20, 1667–1671;
- 3hH.-B. Sun, L. Gong, Y.-B. Tian, J.-G. Wu, X. Zhang, J. Liu, Z. Fu, D. Niu, Angew. Chem. Int. Ed. 2018, 57, 9456–9460; Angew. Chem. 2018, 130, 9600–9604;
- 3iQ. Xiao, L. Tian, R. Tan, Y. Xia, D. Qiu, Y. Zhang, J. Wang, Org. Lett. 2012, 14, 4230–4233;
- 3jT. V. Nykaza, J. C. Cooper, G. Li, N. Mahieu, A. Ramirez, M. R. Luzung, A. T. Radosevich, J. Am. Chem. Soc. 2018, 140, 15200–15205.
- 4C. Sandford, V. K. Aggarwal, Chem. Commun. 2017, 53, 5481–5494.
- 5
- 5aH. C. Brown, K. W. Kim, T. E. Cole, B. Singaram, J. Am. Chem. Soc. 1986, 108, 6761–6764;
- 5bD. S. Matteson, G. Y. Kim, Org. Lett. 2002, 4, 2153–2155;
- 5cB. J. Kim, D. S. Matteson, Angew. Chem. Int. Ed. 2004, 43, 3056–3058; Angew. Chem. 2004, 116, 3118–3120;
- 5dV. Bagutski, T. G. Elford, V. K. Aggarwal, Angew. Chem. Int. Ed. 2011, 50, 1080–1083; Angew. Chem. 2011, 123, 1112–1115;
- 5eJ. Pietruszka, G. Solduga, Eur. J. Org. Chem. 2009, 5998–6008.
- 6
- 6aS. N. Mlynarski, A. S. Karns, J. P. Morken, J. Am. Chem. Soc. 2012, 134, 16449–16451;
- 6bE. K. Edelstein, A. C. Grote, M. D. Palkowitz, J. P. Morken, Synlett 2018, 29, 1749–1752.
- 7R. Goesl, A. Meuwsen, Org. Synth. 1963, 43, 1–3.
- 8See detailed analysis in the Supporting Information.
- 9
- 9aY. Hu, W. Sun, T. Zhang, N. Xu, J. Xu, Y. Lan, C. Liu, Angew. Chem. Int. Ed. 2019, 58, 15813–15818; Angew. Chem. 2019, 131, 15960–15965;
- 9bQ. Zhu, Z. He, L. Wang, Y. Hu, C. Xia, C. Liu, Chem. Commun. 2019, 55, 11884–11887;
- 9cZ. He, Q. Zhu, X. Hu, L. Wang, C. Xia, C. Liu, Org. Chem. Front. 2019, 6, 900–907;
- 9dL. Wang, W. Sun, C. Liu, Chin. J. Catal. 2018, 39, 1725–1729;
- 9eW. Sun, L. Wang, C. Xia, C. Liu, Angew. Chem. Int. Ed. 2018, 57, 5501–5505; Angew. Chem. 2018, 130, 5599–5603;
- 9fD. Shi, L. Wang, C. Xia, C. Liu, Angew. Chem. Int. Ed. 2018, 57, 10318–10322; Angew. Chem. 2018, 130, 10475–10479;
- 9gL. Wang, T. Zhang, W. Sun, Z. He, C. Xia, Y. Lan, C. Liu, J. Am. Chem. Soc. 2017, 139, 5257–5264.
- 10P. Rademacher, Sci. Synth. 2009, 40b, 1133–1210.
- 11
- 11aW.-L. Yu, J.-Q. Chen, Y.-L. Wei, Z.-Y. Wang, P.-F. Xu, Chem. Commun. 2018, 54, 1948–1951;
- 11bW.-D. Liu, G.-Q. Xu, X.-Q. Hu, P.-F. Xu, Org. Lett. 2017, 19, 6288–6291;
- 11cJ.-N. Mo, W.-L. Yu, J.-Q. Chen, X.-Q. Hu, P.-F. Xu, Org. Lett. 2018, 20, 4471–4474.
- 12J. L. Stymiest, G. Dutheuil, A. Mahmood, V. K. Aggarwal, Angew. Chem. Int. Ed. 2007, 46, 7491–7494; Angew. Chem. 2007, 119, 7635–7638.
- 13S. Kisan, V. Krishnakumar, C. Gunanathan, ACS Catal. 2017, 7, 5950–5954.
- 14
- 14aJ. B. Morgan, S. P. Miller, J. P. Morken, J. Am. Chem. Soc. 2003, 125, 8702–8703;
- 14bL. Yan, J. P. Morken, Org. Lett. 2019, 21, 3760–3763;
- 14cA. Bonet, C. Pubill-Ulldemolins, C. Bo, H. Gulyás, E. Fernández, Angew. Chem. Int. Ed. 2011, 50, 7158–7161; Angew. Chem. 2011, 123, 7296–7299;
- 14dC. Pubill-Ulldemolins, M. Poyatos, C. Bo, E. Fernández, Dalton Trans. 2013, 42, 746–752;
- 14eF. Alonso, Y. Moglie, L. Pastor-Pérez, A. Sepúlveda-Escribano, ChemCatChem 2014, 6, 857–865.
- 15H. Ito, K. Kubota, Org. Lett. 2012, 14, 890–893.
- 16E. C. Neeve, S. J. Geier, I. A. I. Mkhalid, S. A. Westcott, T. B. Marder, Chem. Rev. 2016, 116, 9091–9161.
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