SIOC 中文
CJOG
Adv search

Chinese Journal of Organic Chemistry >

0 202605030

DOI: https://doi.org/10.6023/cjoc202605030

ARTICLE

Copper-Catalyzed Enantioselective Oxidation of Allylic C-H Bonds

  • Li Jiayuan ,
  • Chen Pinhong ,
  • Liu Guosheng
Expand
  • aNew Cornerstone Science Laboratory, State Key Laboratory of Organometallic Chemistry, and Shanghai-Hong Kong Joint Laboratory in Chemical Synthesis, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032, China.

Received date: 2026-05-30

  Revised date: 2026-07-13

  Online published: 2026-07-24

Supported by

National Key R&D Program of China (No. 2021YFA1500100), the Strategic Priority Research Program of the Chinese Academy of Sciences (No. XDB0610000), the National Nature Science Foundation of China (Nos. 22331012, 22561160127, and 92256301), and Shanghai Pilot Program for Basic Research. G.L. acknowledges support from the New Cornerstone Science Foundation.

Fold

Abstract

Enantioselective allylic C-H oxidation represents an attractive strategy for the synthesis of chiral allylic oxygenated compounds. However, the development of catalytic asymmetric variants remains challenging due to the inherent inertness of C-H bonds and the difficulty in controlling stereoselectivity during C-H functionalization. Herein, we report a copper-catalyzed enantioselective allylic C-H oxidation that enables the direct synthesis of chiral allylic esters from simple alkenes. The reaction employs a chiral ligand-supported copper catalyst in combination with an N-Cl reagent to generate an N-centered radical capable of selective hydrogen atom transfer (HAT) to the allylic position of alkenes, forming an allylic radical intermediate. Subsequent capture of this radical by a copper-carboxylate species enables enantioselective C-O bond formation, affording the desired chiral allylic esters. The transformation proceeds under mild conditions and exhibits a broad substrate scope, accommodating both cyclic and acyclic alkenes with moderate to good yields and high levels of enantioselectivity. Notably, the reaction can be conducted with the alkene as the limiting reagent, addressing a common limitation of traditional allylic oxidation methods.

Key words： allylic C-H oxidation; asymmetric catalysis; copper catalysis; hydrogen atom transfer (HAT); chiral allylic ester

Cite this article

Li Jiayuan , Chen Pinhong , Liu Guosheng . Copper-Catalyzed Enantioselective Oxidation of Allylic C-H Bonds[J]. Chinese Journal of Organic Chemistry, 0 : 202605030 . DOI: 10.6023/cjoc202605030

References

[1] Cernak, T.; Dykstra, K. D.; Tyagarajan, S.; Vachal, P.; Krska, S. W.Chem. Soc. Rev. 2016, 45, 546-576.
[2] Guillemard, L.; Kaplaneris, N.; Ackermann, L.; Johansson, M. J.Nat. Rev. Chem. 2021, 5, 522-545.
[3] Santaniello, E., Ferraboschi, P., Grisenti, P. & Manzocchi, A.Chem. Rev. 1992, 92, 1071-1140.
[4] Giri, R.; Shi, B. F.; Engle, K. M.; Maugel, N.; Yu, J.-Q.Chem. Soc. Rev. 2009, 38, 3242-3272.
[5] Sun, C.-L.; Li, B.-J.; Shi, Z.-J.Chem. Rev. 2011, 111, 1293-1314.
[6] Hartwig, J. F.; Larsen, M. A.ACS Cent. Sci. 2016, 2, 281-292.
[7] White, M. C.; Zhao, J.J. Am. Chem. Soc. 2018, 140, 13988-14009.
[8] Cheng, S.; Li, Q.; Cheng, X. L.; Lin, Y. M.; Gong, L.Chin. J. Chem. 2022, 40, 2825-2837.
[9] Qian, P.-F.; Shi, B.-F.Chem. Sci. 2026, 17, 2969-2989.
[10] Chakrabarty S.; Wang Y.; Perkins J. C.; Narayan, A. R. H. Chem. Soc. Rev.2020, 49, 8137-8155.
[11] Golden, D. L., Suh, S.-E.; Stahl, S. S. Nat. Rev. Chem.2022, 6, 405-427.
[12] Che, C.-M., Lo, V. K.-Y., Zhou, C.-Y.; Huang, J.-S. Chem. Soc. Rev. 2011, 40, 1950-1975.
[13] Milan, M., Salamone, M., Costas, M. & Bietti, M. Acc. Chem. Res. 2018, 51, 1984-1995.
[14] Chen M. S.; White M. C. Science2010, 327, 566-571.
[15] Qin, Y.; Zhu, L. H.; Luo, S.Chem. Rev. 2017, 117, 9433-9520.
[16] Cao M.; Sun H.-R.; Liu, L. Sci China Chem,2025, 68, 5429-5450.
[17] Rittle, J.; Green, M. T.Science 2010, 330, 933-937.
[18] Wang X.; Chen J.; Ma N.; Cong, Z. Acta Chim. Sinica2020, 78, 490-503
[19] Yang, Y.; Arnold, F. H.Acc. Chem. Res. 2021, 54, 1209-1225.
[20] Liu, W.; Groves, J. T.Acc. Chem. Res. 2015, 48, 1727-1735.
[21] Zaragoza, J. P. T.; Siegler, M. A.; Goldberg, D. P.J. Am. Chem. Soc. 2018, 140, 4380-4390.
[22] Gu, Y.; Natoli, S. N.; Liu, Z.; Clark, D. S.; Hartwig, J. F.Angew. Chem., Int. Ed. 2019, 58, 13954-13960.
[23] Huang, X.; Groves, J. T.Chem. Rev. 2018, 118, 2491-2553.
[24] Kawasaki, K.-i.; Katsuki, T.Tetrahedron 1997, 53, 6337-6350.
[25] Wang, F.0[25] Wang, F.; Chen, P.; Liu, G. Acc. Chem. Res. 2018, 51, 2036-2046.
[26] Zhang, Z.; Chen, P.; Liu, G.Chem. Soc. Rev. 2022, 51, 1640-1658.
[27] Wang, F.; Chen, P.; Liu, G.Nat. Synth. 2022, 1, 107-116.
[28] Ling T.; Qin H.; Liu, F. Chin. J. Org. Chem.2025, 45, 498-515 (in Chinese).
令天鹏, 秦海涛, 刘峰有机化学, 2025, 45, 498-515.
[29] Kharasch, M. S.; Sosnovsky, G.J. Am. Chem. Soc. 1958, 80, 756-756.
[30] Kharasch, M. S.; Fono, A.J. Org. Chem. 1958, 23, 324-324.
[31] Kharasch, M. S.; Sosnovsky, G.; Yang, N. C.J. Am. Chem. Soc.1959, 81, 5819-5824.
[32] Andrus M. B.; Lashley J. C. Tetrahedron2002, 58, 845-866.
[33] Zhang B.; Zhu S.-F.; Zhou Q.-L. Tetrahedron Lett.2013, 54, 2665-2668.
[34] Chen, X.; Li, H.-H.; Kramer, S.Angew. Chem., Int. Ed. 2024, 63, e202413190.
[35] Tang, S.; Xu, H.; Dang, Y.; Yu, S.J. Am. Chem. Soc. 2024, 146, 27196-27203.
[36] Liu, X.-M.; Li, F.; Wang, T.; Dai, L.; Yang, Y.; Jiang, N.-Q.; Xue, L.-Y.; Liu, J.-Y.; Xue, X.-S.; Xiao, L.-J.; Zhou, Q.-L.J. Am. Chem. Soc. 2025, 147, 627-635
[37] Zhang, H.; Zhou, Y.; Yang, T.; Wu, J.; Chen, P.; Lin, Z.; Liu, G.Nat. Catal. 2025, 8, 58-66.
[38] Zhou Y.; Chen P.; Liu, G. J. Am. Chem. Soc.2025, 147, 22873-22882.
[39] Qi X.-K.; Dai Q.; Gu Y.; Lau K. S.; Sung H. H. Y.; Williams I. D.; Lin Z.; Zhang C.; Sun, J. J. Am. Chem. Soc.2025, 147, 20225-20232.
[40] Li, J.; Zhang, Z.; Wu, L.; Zhang, W.; Chen, P.; Lin, Z.; Liu, G.Nature 2019, 574, 516-521.
[41] Fu, L.; Zhang, Z.; Chen, P.; Lin, Z.; Liu, G.J. Am. Chem. Soc. 2020, 142, 12493-12500.
[42] Cheng, Z.; Yang, T.; Li, C.; Deng, Y.; Zhang, F.; Chen, P.; Lin, Z.; Ma, S.; Liu, G.J. Am. Chem. Soc. 2023, 145, 25995-26002.
[43] Mezei G.; Rivera-Carrillo M.; Raptis, R. G. Inorganica Chimica Acta. 2004, 3573721-3732.
[44] Zhang F.; Yang T.; Cheng Z.; Chen P.; Lin Z.; Liu, G. J. Am. Chem. Soc.2026, 148, 20240-20253.
Options
Outlines

/

〈 〉