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2021 , Vol. 41 >Issue 4: 1572 - 1581

DOI: https://doi.org/10.6023/cjoc202101009

研究论文

无配体参与的铱催化的苄位二级碳氢键的硼化反应

  • 刘路华 ,
  • 杜荣荣 ,
  • 徐森苗
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  • a 中国科学院兰州化学物理研究所 羰基合成与选择氧化国家重点实验室 兰州 730000
    b 中国科学院大学 北京 100049

收稿日期: 2021-01-05

  修回日期: 2021-01-25

  网络出版日期: 2021-02-22

基金资助

国家自然科学基金(21873261)

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Ligand-Free Iridium-Catalyzed Borylation of Secondary Benzylic C—H Bonds

  • Luhua Liu ,
  • Rongrong Du ,
  • Senmiao Xu
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  • a State Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000
    b University of Chinese Academy of Sciences, Beijing 100049
* Corresponding author. E-mail:

Received date: 2021-01-05

  Revised date: 2021-01-25

  Online published: 2021-02-22

Supported by

National Natural Science Foundation of China(21873261)

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摘要

报道了无外加配体参与的以吡唑作为导向基团的铱催化的sp3碳氢键的区域选择性硼化反应. 在催化量的[Ir(OMe)(cod)]2存在下, 该反应能够顺利地将苄位的二级碳氢键转化成碳硼键. 该反应具有非常广谱的官能团兼容性, 能够以良好到优秀的产率生成相应的产物. 此外, 导向基团吡唑能够通过臭氧接转化成酰胺.

关键词： 碳氢键活化; 铱; 合成方法; 硼化

本文引用格式

刘路华 , 杜荣荣 , 徐森苗 . 无配体参与的铱催化的苄位二级碳氢键的硼化反应[J]. 有机化学, 2021 , 41(4) : 1572 -1581 . DOI: 10.6023/cjoc202101009

Abstract

The ligand-free regioselective iridium-catalyzed C(sp3)—H bond borylation using pyrazole as the directing group is reported. The reaction occurs smoothly at the secondary benzylic position in the presence of a catalytic amount of commercially available [Ir(OMe)(cod)]2. A variety of functionalities could be well tolerated, affording corresponding products in good to excellent yields. The pyrazole could be degraded into amide by ozonolysis.

Key words： C—H activation; iridium; synthetic methods; borylation

参考文献

[1]
(a) Cho, J.-Y.; Tse, M.K.; Holmes, D.; Maleczka, R.E.; Smith, M.R. Science 2002, 295,305.
[1]
(b) Ishiyama, T.; Takagi, J.; Ishida, K.; Miyaura, N.; Anastasi, N.R.; Hartwig, J.F. J. Am. Chem. Soc. 2002, 124,390.
[1]
(c) Mkhalid, I.A. I.; Barnard, J.H.; Marder, T.B.; Murphy, J.M.; Hartwig, J.F. Chem. Rev. 2010, 110,890.
[1]
(d) Wang, M.; Shi, Z. Chem. Rev. 2020, 120,7438.
[2]
Boller, T.M.; Murphy, J.M.; Hapke, M.; Ishiyama, T.; Miyaura, N.; Hartwig, J.F. J. Am. Chem. Soc. 2005, 127,14263.
[3]
(a) Ros, A.; Fernández, R.; Lassaletta, J.M. Chem. Soc. Rev. 2014, 43,3229.
[3]
(b) Hartwig, J.F. Chem. Soc. Rev. 2011, 40,1992.
[3]
(c) Xu, L.; Wang, G.; Zhang, S.; Wang, H.; Wang, L.; Liu, L.; Jiao, J.; Li, P. Tetrahedron 2017, 73,7123.
[3]
(d) Jin, J.; Xia, H.; Zhang, F.; Wang, Y. Chin. J. Org. Chem. 2020, 40,2185. (in Chinese)
[3]
( 靳继康, 夏慧敏, 张凤莲, 汪义丰, 有机化学, 2020, 40,2185.)
[3]
(e) Shi, D.; Wang, L.; Xia, C.; Liu, C. Chin. J. Org. Chem. 2020, 40,3605. (in Chinese)
[3]
( 史敦发, 王露, 夏春谷, 刘超, 有机化学, 2020, 40,3605.)
[3]
(f) He, H.; Jiang, Z. Chin. J. Org. Chem. 2020, 40,3483. (in Chinese)
[3]
( 许荷欢, 江智勇, 有机化学, 2020, 40,3483.)
[3]
(g) Zhu, S.; Chu, L. Chin. J. Org. Chem. 2020, 40,3980. (in Chinese)
[3]
( 朱圣卿, 储玲玲, 有机化学, 2020, 40,3980.)
[4]
Selected examples, see: (a) Thongpaen, J; Schmid, T. E.; Toupet, L.; Dorcet, V.; Mauduit, M.; Baslé, O. Chem. Commun. 2018, 54,8202.
[4]
(b) Roering, A.J.; Hale, L.V. A.; Squier, P.A.; Ringgold, M.A.; Wiederspan, E.R.; Clark, T.B. Org. Lett. 2012, 14,3558.
[4]
(c) Xu, F.; Duke, O.M.; Rojas, D.; Eichelberger, H.M.; Kim, R.S.; Clark, T.B.; Watson, D.A. J. Am. Chem. Soc. 2020, 142,11988.
[4]
(d) Nakamura, T.; Suzuki, K.; Yamashita, M. J. Am. Chem. Soc. 2017, 139,17763.
[4]
(e) Wang, G.; Liu, L.; Wang, H.; Ding, Y.-S.; Zhou, J.; Mao, S.; Li, P. J. Am. Chem. Soc. 2017, 139,91.
[4]
(f) Ghaffari, B.; Preshlock, S.M.; Plattner, D.L.; Staples, R.J.; Maligres, P.E.; Krska, S.W.; Maleczka, R.E.; Smith, M.R. J. Am. Chem. Soc. 2014, 136,14345.
[4]
(g) Wright, S.E.; Richardson-Solorzano, S.; Stewart, T.N.; Miller, C.D.; Morris, K.C.; Daley, C.J. A.; Clark, T.B. Angew. Chem. Int. Ed. 2019, 58,2834.
[4]
(h) Kawamorita, S.; Miyazaki, T.; Ohmiya, H.; Iwai, T.; Sawamura, M. J. Am. Chem. Soc. 2011, 133,19310.
[4]
(i) Kawamorita, S.; Ohmiya, H.; Hara, K.; Fukuoka, A.; Sawamura, M. J. Am. Chem. Soc. 2009, 131,5058.
[4]
(j) Ros, A.; Estepa, B.; López-Rodríguez, R.; álvarez, E.; Fernández, R.; Lassaletta, J.M. Angew. Chem. Int. Ed. 2011, 50,11724.
[4]
(k) Ros, A.; López-Rodríguez, R.; Estepa, B.; álvarez, E.; Fernández, R.; Lassaletta, J.M. J. Am. Chem. Soc. 2012, 134,4573.
[5]
Selected examples, see: (a) Liu, L.; Wang, G.; Li, P. Org. Lett. 2017, 19,6132.
[5]
(b) Yang, Y.; Gao, Q.; Xu, S. Adv. Synth. Catal. 2019, 361,858.
[5]
(c) Yamamoto, T.; Ishibashi, A.; Suginome, M. Org. Lett. 2017, 19,886.
[5]
(d) Crawford, K.M.; Ramseyer, T.R.; Daley, C.J. A.; Clark, T.B. Angew. Chem. Int. Ed. 2014, 53,7589.
[5]
(e) Boebel, T.A.; Hartwig, J.F. J. Am. Chem. Soc. 2008, 130,7534.
[6]
Selected examples, see: (a) Zeng, J; Naito, M.; Torigoe, T.; Yamanaka, M.; Kuninobu, Y. Org. Lett. 2020, 22,3485.
[6]
(b) Bai, S.-T.; Bheeter, C.B.; Reek, J.N. H. Angew. Chem. Int. Ed. 2019, 58,13039.
[6]
(c) Roosen, P.C.; Kallepalli, V.A.; Chattopadhyay, B.; Singleton, D.A.; Maleczka, R.E.; Smith, M.R. J. Am. Chem. Soc. 2012, 134,11350.
[6]
(d) Preshlock, S.M.; Plattner, D.L.; Maligres, P.E.; Krska, S.W.; Maleczka, R.E.; Smith, M.R. Angew. Chem. Int. Ed. 2013, 52,12915.
[6]
(e) Smith, M.R.; Bisht, R.; Haldar, C.; Pandey, G.; Dannatt, J.E.; Ghaffari, B.; Maleczka, R.E.; Chattopadhyay, B. ACS Catal. 2018, 8,6216.
[6]
(f) Kuninobu, Y.; Ida, H.; Nishi, M.; Kanai, M. Nat. Chem. 2015, 7,712.
[7]
Chattopadhyay, B.; Dannatt, J.E.; Andujar-De Sanctis, I.L.; Gore, K.A.; Maleczka, R.E.; Singleton, D.A.; Smith, M.R. J. Am. Chem. Soc. 2017, 139,7864.
[8]
(a) Mihai, M.T.; Williams, B.D.; Phipps, R.J. J. Am. Chem. Soc. 2019, 141,15477.
[8]
(b) Davis, H.J.; Genov, G.R.; Phipps, R.J. Angew. Chem. Int. Ed. 2017, 56,13351.
[8]
(c) Davis, H.J.; Mihai, M.T.; Phipps, R.J. J. Am. Chem. Soc. 2016, 138,12759.
[9]
Yang, L.; Semba, K.; Nakao, Y. Angew. Chem. Int. Ed. 2017, 56,4853.
[10]
(a) Liskey, C.W.; Hartwig, J.F. J. Am. Chem. Soc. 2012, 134,12422.
[10]
(b) Oeschger, R.; Su, B.; Yu, I.; Ehinger, C.; Romero, E.; He, S.; Hartwig, J. Science 2020, 368,736.
[10]
(c) Zhong, R.-L.; Sakaki, S. J. Am. Chem. Soc. 2019, 141,9854.
[10]
(d) Larsen, M.A.; Oeschger, R.J.; Hartwig, J.F. ACS Catal. 2020, 10,3415.
[10]
(e) Ohmura, T.; Torigoe, T.; Suginome, M. J. Am. Chem. Soc. 2012, 134,17416.
[10]
(f) Kawamorita, S.; Murakami, R.; Iwai, T.; Sawamura, M. J. Am. Chem. Soc. 2013, 135,2947.
[11]
Cho, S.H.; Hartwig, J.F. J. Am. Chem. Soc. 2013, 135,8157.
[12]
Kang, E.; Kim, H.T.; Joo, J.M. Org. Biomol. Chem. 2020, 18,6192.
[13]
Boerth, J.A.; Hummel, J.R.; Ellman, J.A. Angew. Chem. Int. Ed. 2016, 55,12650.
[14]
(a) Gulia, N.; Daugulis, O. Angew. Chem. Int. Ed. 2017, 56,3630.
[14]
(b) Yang, W.; Ye, S.; Fanning, D.; Coon, T.; Schmidt, Y.; Krenitsky, P.; Stamos, D.; Yu, J.-Q. Angew. Chem. Int. Ed. 2015, 54,2501.
[14]
(c) Shabashov, D.; Daugulis, O. Org. Lett. 2005, 7,3657.
[14]
(d) Hull, K.L.; Sanford, M.S. J. Am. Chem. Soc. 2007, 129,11904.
[14]
(e) Shen, Y.; Cindy Lee, W.-C.; Gutierrez, D.A.; Li, J.J. J. Org. Chem. 2017, 82,11620.
[15]
(a) Ackermann, L.; Althammer, A.; Born, R. Tetrahedron 2008, 64,6115.
[15]
(b) Ackermann, L.; Althammer, A.; Born, R. Angew. Chem. Int. Ed. 2006, 45,2619.
[15]
(c) Hofmann, N.; Ackermann, L. J. Am. Chem. Soc. 2013, 135,5877.
[15]
(d) Wang, Y.; Liu, H.; Li, B.; Wang, B. Adv. Syn. Catal. 2019, 361,1564.
[16]
(a) Yuan, C.; Tu, G.; Zhao, Y. Org. Lett. 2017, 19,356.
[16]
(b) Li, T.; Liu, C.; Wu, S.; Chen, C.; Zhu, B. Org. Biomol. Chem. 2019, 17,7679.
[16]
(c) Cai, H.; Thombal, R.S.; Li, X.; Lee, Y.R. Adv. Synth. Catal. 2019, 361,4022.
[16]
(d) Kim, H.; Thombal, R.S.; Khanal, H.D.; Lee, Y.R. Chem. Commun. 2019, 55,13402.
[16]
(e) Saitou, T.; Jin, Y.; Isobe, K.; Suga, T.; Takaya, J.; Iwasawa, N. Chem. Asian J. 2020, 15,1941.
[17]
Gao, P.; Guo, W.; Xue, J.; Zhao, Y.; Yuan, Y.; Xia, Y.; Shi, Z. J. Am. Chem. Soc. 2015, 137,12231.
[18]
(a) Wang, Y.; Liu, H.; Li, B.; Wang, B. Adv. Synth. Catal. 2019, 361,1564.
[18]
(b) Botla, V.; Akudari, A.; Malapaka, C. Tetrahedron Lett. 2019, 60,115.
[18]
(c) Lee, W.-C. C.; Shen, Y.; Gutierrez, D.A.; Li, J.J. Org. Lett. 2016, 18,2660.
[19]
Crystallographic data for 13 could be found in the Supporting Information. CCDC 2031418 (13) contains the supplementary crystallographic data for this paper. The data can be obtained free of charge from The Cambridge Crystallographic Data Center via .
[20]
Hu, N.; Zhao, G.; Zhang, Y.; Liu, X.; Li, G.; Tang, W. J. Am. Chem. Soc. 2015, 137,6746.
[21]
Liu, Z.; Ni, H.-Q.; Zeng, T.; Engle, K.M. J. Am. Chem. Soc. 2018, 140,3223.
[22]
Kawamorita, S.; Miyazaki, T.; Iwai, T.; Ohmiya, H.; Sawamura, M. J. Am. Chem. Soc. 2012, 134,12924.
[23]
Bonet, A.; Odachowski, M.; Leonori, D.; Essafi, S.; Aggarwal, V.K. Nat. Chem. 2014, 6,584.
[24]
Kremsner, J.M.; Kappe, C.O. J. Org. Chem. 2006, 71,4651.
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