Citation: Cheng Zhongming, Chen Pinhong, Liu Guosheng. Enantioselective Cyanation of Remote C-H Bonds via Cooperative Photoredox and Copper Catalysis[J]. Acta Chimica Sinica, ;2019, 77(9): 856-860. doi: 10.6023/A19070252 shu

Enantioselective Cyanation of Remote C-H Bonds via Cooperative Photoredox and Copper Catalysis

State Key Laboratory of Organometallic Chemistry, andShanghai Hongkong Joint Laboratory in Chemical Synthesis, Center for Excellence in Molecular Synthesis, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032

Corresponding author: Liu Guosheng, gliu@mail.sioc.ac.cn
Received Date: 4 July 2019
Available Online: 15 September 2019
Fund Project: the National Natural Science Foundation of China 21790330the Science and Technology Commission of Shanghai Municipality 17QA1405200the Science and Technology Commission of Shanghai Municipality 17XD1404500the Science and Technology Commission of Shanghai Municipality 17JC1401200the National Natural Science Foundation of China 21532009the National Basic Research Program of China 973-2015CB856600the National Natural Science Foundation of China 21821002Project supported by the National Basic Research Program of China (No. 973-2015CB856600), the National Natural Science Foundation of China (Nos. 21532009, 21790330 and 21821002), the Science and Technology Commission of Shanghai Municipality (Nos. 17XD1404500, 17QA1405200 and 17JC1401200), and the Key Research Program of Frontier Science (No. QYZDJSSWSLH055) of the Chinese Academy of Sciencesthe Key Research Program of Frontier Science QYZDJSSWSLH055

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Optically pure alkylnitriles are important structural motifs found in agrochemicals, pharmaceuticals, and natural products, which can be further transferred to acids, amines and amides. Direct asymmetric cyanation of sp³ C-H bonds represents the most efficient synthetic pathway to these optically pure alkylnitriles. However, selective functionalization of sp³ C-H bonds remains a crucial issue due to the inertness of sp³ C-H bonds as well as the difficulties in the control of stereo-and regioselectivity. Inspired by enzymatic oxygenases and halogenases, such as cytochrome P450 and nonheme iron enzymes, the radical-based C-H functionalization has received much attention, which was initiated with a hydrogen atom transfer (HAT) process. Recently, numerous reports have been disclosed for the highly efficient functionalization of C-H bonds with an intramolecular HAT process as a key step to govern the reactivity and site selectivity. Our group has developed a copper-catalyzed radical relay process for the enantioselective cyanation and arylation of benzylic C-H bonds using TMSCN and ArB(OH)₂ as nucleophiles respectively. Mechanistic studies indicated that a benzylic radical generated via a radical replay process can be trapped by a reactive chiral copper(Ⅱ) cyanide enantioselectively, delivering optically pure benzyl nitriles efficiently. Herein, we communicate the catalytic asymmetric cyanation of remote C-H bonds by merging photoredox catalysis with copper catalysis. This reaction proceeds under mild reaction conditions and exhibits good functional group compatibility as well as wide substrates scope. Additionally, the nitrile group was further reduced to amide under hydrogen atmosphere. This reaction provides an efficient pathway to synthesize chiral δ-cyano alcohols and 1, 6-amino alcohols. The general procedure is as following:in a dried sealed tube, substrate 1 (0.2 mmol, 1.0 equiv.), Cu(CH₃CN)₄PF₆ (0.01 mmol, 5 mol%), L (0.015 mmol, 7.5 mol%) and Ir(ppy)₃ (0.002 mmol, 1 mol%) were dissolved in dichloromethane (4.0 mL) under N₂ atmosphere, and stirred for 30 min. Then, TMSCN (50 μL, 0.4 mmol, 2 equiv.) was added slowly under N₂ atmosphere. The tube was sealed with a Teflon-lined cap, and the mixture was stirred under the irradiation of blue LED for 1~7 d. The reaction mixture was diluted with dichloromethane, filtered through a short pad of celite. A solution of TBAF (3 equiv.) and HOAc (3 equiv.) was added to the filtration. The mixture was stirred for 5 min and then washed with water (3×10 mL) and dried over anhydrous Na₂SO₄. After filtration and concentration, the residue was purified by silica gel chromatography (eluent:petroleum ether/ethyl acetate) to afford target product.
- enantioselective cyanation,
- C-H bonds,
- copper catalysis,
- photoredox catalysis,
- 1, 5-hydrogen atom transfer
1. [1]
2. [2]
  (a) Rappoport, Z. The Chemistry of the Cyano Group, Interscience Publishers, London, 1970. (b) Larock, R. C. Comprehensive Organic Transformations: A Guide to Functional Group Preparation, 2nd ed., Wiley-VCH, Weinheim, 1999, p. 821.
3. [3]
  Cernak, T.; Dykstra, K. D.; Tyagarajan, S.; Vachal, P.; Krska, S. W. Chem. Soc. Rev. 2016, 45, 546. doi: 10.1039/C5CS00628G
4. [4]
  (a) Meunier, B.; de Visser, S. P.; Shaik, S. Chem. Rev. 2004, 104, 3947. (b) Ortiz de Montellano, P. R. Chem. Rev. 2010, 110, 932.
5. [5]
6. [6]
  For some reviews, see:Stateman, L. M.; Nakafuku, K. M.; Nagib, D. A. Synthesis 2018, 50, 1569. doi: 10.1055/s-0036-1591930
7. [7]
  (a) Martínez, C.; Muñiz, K. Angew. Chem., Int. Ed. 2015, 54, 8287. (b) Choi, G. J.; Zhu, Q.; Miller, D. C.; Gu, C. J.; Knowles, R. R. Nature 2016, 539, 268. (c) Chu, J. C. K.; Rovis, T. Nature 2016, 539, 272. (d) Chen, D.; Chu, J. C. K.; Rovis, T. J. Am. Chem. Soc. 2017, 139, 14897. (e) Wappes, E. A.; Fosu, S. C.; Chopko, T. C.; Nagib, D. A. Angew. Chem., Int. Ed. 2016, 55, 9974. (f) Liu, T.; Myers, M. C.; Yu, J.-Q. Angew. Chem., Int. Ed. 2017, 56, 306. (g) Becker, P.; Duhamel, T.; Stein, C. J.; Reiher, M.; Muñiz, K. Angew. Chem., Int. Ed. 2017, 56, 8004. (h) Li, Z.; Wang, Q.; Zhu, J. Angew. Chem., Int. Ed. 2018, 57, 13288. (i) Jiang, H.; Studer, A. Angew. Chem., Int. Ed. 2018, 57, 1692. (j) Xia, Y.; Wang, L.; Studer, A. Angew. Chem., Int. Ed. 2018, 57, 12940. (k) Dauncey, E. M.; Morcillo, S. P.; Douglas, J. J.; Sheikh, N. S.; Leonori, D. Angew. Chem., Int. Ed. 2018, 57, 744. (l) Morcillo, S. P.; Dauncey, E. M.; Kim, J. H.; Douglas, J. J.; Sheikh, N. S.; Leonori, D. Angew. Chem., Int. Ed. 2018, 57, 12945. (m) Li, C.; Lang, K.; Lu, H.; Hu, Y.; Cui, X.; Wojtas, L.; Zhang, X. P. Angew. Chem., Int. Ed. 2018, 57, 16837. (n) Chen, H.; Guo, L.; Yu, S. Org. Lett. 2018, 20, 6255. (o) Stateman, L. M.; Wappes, E. A.; Nakafuku, K. M.; Edwards, K. M.; Nagib, D. A. Chem. Sci. 2019, 10, 2693. (p) Zhang, Z.; Stateman, L. M.; Nagib, D. A. Chem. Sci. 2019, 10, 1207. (q) Wu, K.; Wang, L.; Colón-Rodríguez, S.; Flechsig, G.-U.; Wang, T. Angew. Chem., Int. Ed. 2019, 58, 1774. (r) Bao, X.; Wang, Q.; Zhu, J. Nature Commun. 2019, 10, 768. (s) Lang, K.; Torker, S.; Wojtas, L.; Zhang, X. P. J. Am. Chem. Soc. 2019, DOI: 10.1021/jacs.9b05850.
8. [8]
  (a) Peng, Y.; Lin, J.-S.; Li, L.; Zheng, S.-C.; Xiong, Y.-P.; Zhao, L.-J.; Tan, B.; Liu, X.-Y. Angew. Chem., Int. Ed. 2014, 53, 11890. (b) Zhang, J.; Li, Y.; Zhang, F.; Hu, C.; Chen, Y. Angew. Chem., Int. Ed. 2016, 55, 1872. (c) Wang, C. Y.; Harms, K.; Meggers, E. Angew. Chem., Int. Ed. 2016, 55, 13495. (d) Hu, A.; Guo, J.-J.; Pan, H.; Tang, H.; Gao, Z.; Zuo, Z. J. Am. Chem. Soc. 2018, 140, 1612. (e) Zhu, Y.; Huang, K.; Pan, J.; Qiu, X.; Luo, X.; Qin, Q.; Wei, J.; Wen, X.; Zhang, L.; Jiao, N. Nat. Commun. 2018, 9, 2625. (f) Wu, X.; Zhang, H.; Tang, N.; Wu, Z.; Wang, D.; Ji, M.; Xu, Y.; Wang, M.; Zhu, C. Nat. Commun. 2018, 9, 3343. (g) Wu, X.; Wang, M.; Huan, L.; Wang, Wang, D. J.; Zhu, C. Angew. Chem., Int. Ed. 2018, 57, 1640. (h) Wang, M.; Huang, L.; Zhu, C. Org. Lett. 2019, 21, 821. (i) Kim, I.; Park, B.; Kang, G.; Kim, J.; Jung, H.; Lee, H.; Baik, M.; Hong, S. Angew. Chem., Int. Ed. 2018, 57, 15517. (j) Guan, H.; Sun, S.; Mao, Y.; Chen, L.; Lu, R.; Huang, J.; Liu, L. Angew. Chem. Int. Ed. 2018, 57, 11413. (k) Bao, X.; Wang, Q.; Zhu, J. Angew. Chem. Int. Ed. 2019, 58, 2139.
9. [9]
  (a) Yu, P.; Zheng, S.-C.; Yang, N.-Y.; Tan, B.; Liu, X.-Y. Angew. Chem., Int. Ed. 2015, 54, 4041. (b) Cui, X.; Xu, X.; Jin, L.-M.; Wojtasa, L.; Zhang, X. P. Chem. Sci. 2015, 6, 1219. (c) Chen, J.-Q.; Wei, Y.-L.; Xu, G.-Q.; Liang, Y.-M.; Xu, P.-F. Chem. Commun. 2016, 52, 6455. (d) Li, T.; Yu, P.; Lin, J.-S.; Zhi, Y.; Liu, X.-Y. Chin. J. Chem. 2016, 34, 490. (e) Li, L.; Ye, L.; Ni, S.-F.; Li, Z.-L.; Chen, S.; Du, Y.-M.; Li, X.-H.; Dang, L.; Liu, X.-Y. Org. Chem. Front. 2017, 4, 2139. (f) Yuan, W.; Zhou. Z.; Gong, L.; Meggers, E. Chem. Commun. 2017, 53, 8964. (g) Li, T.; Yu, P.; Du, Y.-M.; Lin, J.-S.; Zhi, Y.; Liu, X.-Y. J. Fluorine Chem. 2017, 203, 210. (h) Wang, N.; Ye, L.; Li, Z.-L.; Li, L.; Li, Z.; Zhang, H.-X.; Guo, Z.; Gu, Q.-S.; Liu, X.-Y. Org. Chem. Front. 2018, 5, 2810. (i) Chen, J.-Q.; Chang, R.; Lin, J.-B.; Luo, Y.-C.; Xu, P.-F. Org. Lett. 2018, 20, 2395. (j) Wang, Y.; Wen, X.; Cui, X.; Zhang, X. P. J. Am. Chem. Soc. 2018, 140, 4792. (k) Wen, X.; Wang, Y.; Zhang, X. P. Chem. Sci. 2018, 9, 5082. (l) Wu, S.; Wu, X.; Wang, D.; Zhu, C. Angew. Chem., Int. Ed. 2019, 58, 1499. (m) Chuentragool, P.; Yadagiri, D.; Morita, T.; Sarkar, S.; Parasram, M.; Wang, Y.; Gevorgyan, V. Angew. Chem. Int. Ed. 2019, 58, 1794.
10. [10]
  Wang, F.; Chen, P.; Liu, G. Acc. Chem. Res. 2018, 51, 2036. doi: 10.1021/acs.accounts.8b00265
11. [11]
  (a) Zhang, W.; Wang, F.; McCann, S. D.; Wang, D.; Chen, P.; Stahl, S. S.; Liu, G. Science 2016, 353, 1014. (b) Zhang, W.; Wu, L.; Chen, P.; Liu, G. Angew. Chem., Int. Ed. 2019, 58, 6425. (c) Zhang, W.; Chen, P.; Liu, G. J. Am. Chem. Soc. 2017, 139, 7709.
12. [12]
  For cyanations, see: (a) Wang, F.; Wang, D.; Wan, X.; Wu, L.; Chen, P.; Liu, G. J. Am. Chem. Soc. 2016, 138, 15547. (b) Wang, D.; Wang, F.; Chen, P.; Lin, Z.; Liu, G. Angew. Chem., Int. Ed. 2017, 56, 2054. (c) Lu, F.-D.; Liu, D.; Zhu, L.; Lu, L.-Q.; Yang, Q.; Zhou, Q.-Q.; Wei, Y.; Lan, Y.; Xiao, W.-J. J. Am. Chem. Soc. 2019, 141, 6167. For arylations, see: (d) Wu, L.; Wang, F.; Wan, X.; Wang, D.; Chen, P.; Liu, G. J. Am. Chem. Soc. 2017, 139, 2904. (e) Wang, D.; Wu, L.; Wang, F.; Wan, X.; Chen, P.; Lin, Z.; Liu, G. J. Am. Chem. Soc. 2017, 139, 6811. For alkynylation, see: (f) Fu, L.; Zhou, S.; Wan, X.; Chen, P.; Liu, P. J. Am. Chem. Soc. 2018, 140, 10965.
13. [13]
  Wang, D.; Zhu, N.; Chen, P.; Lin, Z.; Liu, G. J. Am. Chem. Soc. 2017, 139, 15632. doi: 10.1021/jacs.7b09802
14. [14]
  (a) Curran, D. P.; Kim, D.; Liu, H. T.; Shen, W. J. Am. Chem. Soc. 1988, 110, 5900. (b) Kim, S.; Lee, T. A.; Song, Y. Synlett 1998, 471. (c) Zlotorzynska, M.; Sammis, G. M. Org. Lett. 2011, 13, 6264.
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