钯催化惰性亚甲基C(sp3)—H键分子间官能团化反应

doi:10.6023/cjoc202406012

摘要/Abstract

尽管过渡金属催化的亚甲基C(sp³)—H官能团化是一项巨大的挑战, 但近年来已取得一系列显著进展. 此文综述了钯催化的惰性亚甲基C(sp³)—H键的分子间官能化反应, 讨论了包括芳基化、烷基化、烯基化/炔基化、乙酰氧基化、胺化、卤化、硼化和硅化在内的多种反应. 由于亚甲基C(sp³)—H键的惰性特性, 其官能化反应通常依赖于导向基策略, 这不仅能控制区域选择性, 还能解决低反应性问题. 各种导向基, 包括强配位的双齿辅助基和弱配位的天然官能团, 已被证明在实现亚甲基C(sp³)—H官能化方面是有效的.

关键词: 钯催化, 碳氢键活化, 亚甲基C(sp³)—H键活化, 交叉偶联

Although transition metal-catalyzed methylene C(sp³)—H functionalization is a great challenge, it has made noticeable progress in recent years. This review specifically describes Pd-catalyzed intermolecular functionalization of unactivated methylene C(sp³)—H bonds. A variety of reactions, including arylation, alkylation, alkenylation/alkynylation, acetoxylation, amination, halogenation, borylation, and silylation reactions, have been discussed. Due to the inert properties, methylene C(sp³)—H functionalization reaction usually relies on the use of directing group strategies, which can not only control regioselectivity but also address low reactivity issue. Various directing groups, including strongly coordinating bidentate auxiliaries and weakly coordinating innate functional groups, have proven to be eﬀective for enabling methylene C(sp³)—H functionalization.

Key words: palladium catalysis, C—H activation, methylene C(sp³)—H activation, cross-coupling

引用此文

梅明顺, 张扬会. 钯催化惰性亚甲基C(sp³)—H键分子间官能团化反应[J]. 有机化学, 2025, 45(2): 620-640.

Mingshun Mei, Yanghui Zhang. Palladium-Catalyzed Intermolecular Functionalization of Unactivated Methylene C(sp³)—H Bonds[J]. Chinese Journal of Organic Chemistry, 2025, 45(2): 620-640.

导出引用 EndNote|Reference Manager|ProCite|BibTeX|RefWorks

分享此文

图/表 54

Scheme 1. Intermolecular functionalization reactions of inert methylene C(sp3)—H bonds

Scheme 2. Directing group-assisted C(sp3)—H arylation

Scheme 3. 8-AQ-directed C(sp3)—H arylation reactions

Scheme 4. 8-AQ-directed enantioselective C(sp3)—H arylation reactions

Scheme 5. 8-AQ-directed C(sp3)—H arylation reaction with diaryliodonium triflates

Scheme 6. N,N-bidentate ligand-directed C(sp3)—H arylation reactions

Scheme 7. PIP-directed enantioselective C(sp3)—H arylation reactions

Scheme 8. β-C(sp3)—H arylation directed by 2,2-dimethyl aminooxyacetic acid

Scheme 9. 8-AQ-directed C(sp3)—H arylation reactions of aliphatic cycloalkanes

Scheme 10. 8-AQ-directed C(sp3)—H arylation reactions of glycosyl carboxamides

Scheme 11. PA-directed C(sp3)—H arylation reactions of cycloalkanes

Scheme 12. Mechanism of transient directing group-assisted C(sp3)—H functionalization

Scheme 13. TDG-Assisted β-C—H arylation of aliphatic aldehydes

Scheme 14. Ligand-controlled regioselective C—H arylation of aliphatic aldehydes

Scheme 15. Ligand-enhanced C—H diarylation of cyclohexanecarboxaldehyde

Scheme 16. TDG-assisted C—H arylation reactions of aliphatic ketones

Scheme 17. TDG-assisted C—H arylation reactions of linear aliphatic amines

Scheme 18. 1-Aminopyridinium-Ylide-directed β-C(sp3)—H arylation

Scheme 19. Amide-directed enantioselective arylation of methylene C—H bonds

Scheme 20. Mechanism of enantioselective C(sp3)—H arylation of cycloalkyl carboxamides

Scheme 21. Amide-directed remote C(sp3)—H arylation reactions of azacycloalkanes

Scheme 22. C(sp3)—H arylation reactions using carbon dioxide as a transient directing group

Scheme 23. Ligand-promoted β-methylene C(sp3)—H arylation of free aliphatic acids

Scheme 24. Ligand-promoted [2＋2] cycloaddition and double methylene C—H arylation reactions and proposed mechanism

Scheme 25. Ligand-promoted methylene C(sp3)—H arylation reactions of cycloalkanes

Scheme 26. Ligand-enabled double γ-C(sp3)—H functionalization of aliphatic acids: one-step synthesis of γ-arylated γ-lactones of this transformation

Scheme 27. Hydrogen-bond-acceptor ligands enable distal C(sp3)—H arylation of free alcohols

Scheme 28. 8-AQ-directed alkylation of C(sp3)—H bonds

Scheme 29. PA-directed alkylation of C(sp3)—H bonds with alkyl iodides

Scheme 30. Ligand-promoted site-selective cyanomethylation of C(sp3)—H bonds with acetonitrile

Scheme 31. PA-directed γ-C(sp3)—H alkenylation reactions of aliphatic cycloalkanes derivatives

Scheme 32. Tandem asymmetric C(sp3)—H alkenylation/aza-Wacker-type cyclization reaction

Scheme 33. C(sp3)—H alkenylation reactions of α-amino acids and peptides with glycosyl iodides

Scheme 34. Silver-free C(sp3)—H alkenylation reactions

Scheme 35. Methylene C(sp3)—H alkynylation reactions

Scheme 36. Alkynylation of methylene C(sp3)—H bonds in aliphatic chains and cycloalkanes

Scheme 37. Enantioselective methylene C(sp3)—H alkynylation reactions

Scheme 38. Carbonylation of methylene C(sp3)—H bonds to synthesize trans-disubstituted β-lactam derivatives

Scheme 39. Oxime ether-directed acetoxylation of methylene C(sp3)—H bonds

Scheme 40. 8-AQ-directed acetoxylation of methylene C(sp3)— H bonds

Scheme 41. Oxime ether-directed acetoxylation of methylene C(sp3)—H bond

Scheme 42. Diastereoselective β-C(sp3)—H acetoxylation of chiral amino acid derivatives

Scheme 43. Alkoxylation of methylene C(sp3)—H bonds with cyclic hypervalent iodine (I3＋) oxidants

Scheme 44. PIP-directed alkoxylation of methylene C(sp3)—H bonds

Scheme 45. Amination of methylene C(sp3)—H bonds

Scheme 46. Amide-directed fluorination of methylene C(sp3)—H bonds in amino acid derivatives

Scheme 47. PIP-directed fluorination of methylene C(sp3)—H bonds

Scheme 48. Oxime ether-directed fluorination of methylene C(sp3)—H bonds

Scheme 49. TDG-mediated fluorination of methylene C(sp3)— H bonds

Scheme 50. Amide-directed borylation of methylene C(sp3)—H bonds

Scheme 51. 8-AQ-directed silylation of methylene C(sp3)—H bonds in cycloalkanes

Scheme 52. 8-AQ-directed silylation of methylene C(sp3)—H bonds

Scheme 53. Pd(0)-catalyzed intermolecular methylene C(sp3)— H silylation by using NHC ligands

Scheme 54. Direct deuteration of methylene C(sp3)—H bonds

参考文献 84

[1]	(a) Li, B.-J.; Shi, Z.-J. Chem. Soc. Rev. 2012, 41, 5588.
	(b) Chu, J. C. K.; Rovis, T. Angew. Chem., Int. Ed. 2018, 57, 62.
	(c) Chen, Z.; Rong, M.-Y.; Nie, J.; Zhu, X.-F.; Shi, B.-F.; Ma, J.-A. Chem. Soc. Rev. 2019, 48, 4921.
	(d) Zhang, Y.-H.; Shi, G.-F.; Yu, J.-Q. In Comprehensive Organic Synthesis, 2nd ed.; Ed.: Molander, G., Knochel, P., Elsevie, Oxford, U.K., 2014, Vol. 3, p. 1101.
[2]	He, J.; Wasa, M.; Chan, K. S. L.; Shao, Q.; Yu, J.-Q. Chem. Rev. 2017, 117, 8754.
[3]	(a) Herrmann, P.; Bach, T. Chem. Soc. Rev. 2011, 40, 2022. doi: 10.1039/c0cs00027b pmid: 28125210
	(b) Dong, Z.; Ren, Z.; Thompson, S. J.; Xu, Y.; Dong, G. Chem. Rev. 2017, 117, 9333. doi: 10.1021/acs.chemrev.6b00574 pmid: 28125210
	(c) Antermite, D.; Bull, J. A. Synthesis 2019, 51, 3171. pmid: 28125210
	(d) Mishra, A. A.; Subhedar, D.; Bhanage, B. M. Chem. Rec. 2019, 19, 1829. pmid: 28125210
	(e) Lucas, E. L.; Lam, N. Y. S.; Zhuang, Z.; Chan, H. S. S.; Strassfeld, D. A.; Yu, J.-Q. Acc. Chem. Res. 2022, 55, 537. pmid: 28125210
	(f) Chen, X.; Li, B.; Tong, H.; Qi, L.; He, G.; Chen, G. Chin. J. Chem. 2022, 40, 2502. pmid: 28125210
	(g) Wang, P.-S.; Gong, L.-Z. Chin. J. Chem. 2023, 41, 1841. pmid: 28125210
	(h) Han, Y. Q.; Shi, B.-F. Acta Chim. Sinica 2023, 81, 1522. pmid: 28125210
	(i) Yoo, W.-J.; Li, C.-J. In C—H Activation, Ed.: Yu, J.-Q.; Shi, Z., Springer Berlin Heidelberg, Berlin, Heidelberg, 2010, p. 281. pmid: 28125210
[4]	(a) Wasa, M.; Engle, K. M.; Lin, D. W.; Yoo, E. J.; Yu, J.-Q. J. Am. Chem. Soc. 2011, 133, 19598. pmid: 32605367
	(b) Xiao, K.-J.; Lin, D. W.; Miura, M.; Zhu, R.-Y.; Gong, W.; Wasa, M.; Yu, J.-Q. J. Am. Chem. Soc. 2014, 136, 8138. pmid: 32605367
	(c) Chan, K. S. L.; Fu, H.-Y.; Yu, J.-Q. J. Am. Chem. Soc. 2015, 137, 2042. pmid: 32605367
	(d) Wu, Q.-F.; Wang, X.-B.; Shen, P.-X.; Yu, J.-Q. ACS Catal. 2018, 8, 2577. pmid: 32605367
	(e) Shen, P.-X.; Hu, L.; Shao, Q.; Hong, K.; Yu, J.-Q. J. Am. Chem. Soc. 2018, 140, 6545. pmid: 32605367
	(f) Hu, L.; Shen, P.-X.; Shao, Q.; Hong, K.; Qiao, J. X.; Yu, J.-Q. Angew. Chem. Int. Ed. 2019, 58, 2134. pmid: 32605367
	(g) Xiao, L.-J.; Hong, K.; Luo, F.; Hu, L.; Ewing, W. R.; Yeung, K.-S.; Yu, J.-Q. Angew. Chem. Int. Ed. 2020, 59, 9594. pmid: 32605367
	(h) Zhuang, Z.; Yu, J.-Q. J. Am. Chem. Soc. 2020, 142, 12015. doi: 10.1021/jacs.0c04801 pmid: 32605367
[5]	Campos, K. R. Chem. Soc. Rev. 2007, 36, 1069. doi: 10.1039/b607547a pmid: 17576475
[6]	(a) Zhang, F.-L.; Hong, K.; Li, T.-J.; Park, H.; Yu, J.-Q. Science 2016, 351, 252.
	(b) Park, H.; Verma, P.; Hong, K.; Yu, J.-Q. Nat. Chem. 2018, 10, 755.
	(c) Mei, M.-S.; Zhang, Y. Org. Lett. 2023, 25, 4985.
[7]	(a) Lyons, T. W.; Sanford, M. S. Chem. Rev. 2010, 110, 1147.
	(b) Song, G. Y.; Li, X. W. Acc. Chem. Res. 2015, 48, 1007.
	(c) He, G.; Wang, B.; Nack, W. A.; Chen, G. Acc. Chem. Res. 2016, 49, 635.
	(d) Zhang, Q.; Shi, B.-F. Acc. Chem. Res. 2021, 54, 2750.
	(e) Babu, S. A.; Aggarwal, Y.; Patel, P.; Tomar, R. Chem. Commun. 2022, 58, 2612.
	(f) He, Y.; Huang, Z.; Wu, K.; Ma, J.; Zhou, Y.-G.; Yu, Z. Chem. Soc. Rev. 2022, 51, 2759.
	(g) Das, J.; Ali, W.; Maiti, D. Trends Chem. 2023, 5, 551.
	(h) Yang, X.; Liu, X.; Wang, L. Chin. J. Org. Chem. 2023, 43, 914 (in Chinese).
	(杨幸, 刘旭, 王丽佳, 有机化学, 2023, 43, 914.) doi: 10.6023/cjoc202211041
[8]	(a) Jin, L.; Wang, J.; Dong, G. Angew. Chem., Int. Ed. 2018, 57, 12352.
	(b) Liu, B.; Romine, A. M.; Rubel, C. Z.; Engle, K. M.; Shi, B.-F. Chem. Rev. 2021, 121, 14957.
[9]	Zaitsev, V. G.; Shabashov, D.; Daugulis, O. J. Am. Chem. Soc. 2005, 127, 13154.
[10]	Shabashov, D.; Daugulis, O. J. Am. Chem. Soc. 2010, 132, 3965. doi: 10.1021/ja910900p pmid: 20175511
[11]	Reddy, B. V. S.; Reddy, L. R.; Corey, E. J. Org. Lett. 2006, 8, 3391.
[12]	Yan, S.-B.; Zhang, S.; Duan, W.-L. Org. Lett. 2015, 17, 2458.
[13]	Tong, H.-R.; Zheng, S.; Li, X.; Deng, Z.; Wang, H.; He, G.; Peng, Q.; Chen, G. ACS Catal. 2018, 8, 11502.
[14]	Huang, Y.; Lv, X.; Tong, H.-R.; He, W.; Bai, Z.; Wang, H.; He, G.; Chen, G. Org. Lett. 2024, 26, 94. doi: 10.1021/acs.orglett.3c03688 pmid: 38149595
[15]	Pan, F.; Shen, P.-X.; Zhang, L.-S.; Wang, X.; Shi, Z.-J. Org. Lett. 2013, 15, 4758.
[16]	Gou, Q.; Zhang, Z.-F.; Liu, Z.-C.; Qin, J. J. Org. Chem. 2015, 80, 3176.
[17]	(a) Ling, P.-X.; Fang, S.-L.; Yin, X.-S.; Chen, K.; Sun, B.-Z.; Shi, B.-F. Chem.-Eur. J. 2015, 21, 17503.
	(b) Chen, K.; Li, Z.-W.; Shen, P.-X.; Zhao, H.-W.; Shi, Z.-J. Chem.-Eur. J. 2015, 21, 7389.
[18]	Luo, F.; Yang, J.; Li, Z.; Xiang, H.; Zhou, X. Adv. Synth. Catal. 2016, 358, 887.
[19]	Lou, J.; Wang, Q.; He, Y.; Yu, Z. Adv. Synth. Catal. 2018, 360, 4571.
[20]	Yan, S.-Y.; Han, Y.-Q.; Yao, Q.-J.; Nie, X.-L.; Liu, L.; Shi, B.-F. Angew. Chem., Int. Ed. 2018, 57, 9093.
[21]	Han, Y.-Q.; Yang, X.; Kong, K.-X.; Deng, Y.-T.; Wu, L.-S.; Ding, Y.; Shi, B.-F. Angew. Chem., Int. Ed. 2020, 59, 20455.
[22]	Zhu, R.-Y.; Liu, L.-Y.; Park, H. S.; Hong, K.; Wu, Y.; Senanayake, C. H.; Yu, J.-Q. J. Am. Chem. Soc. 2017, 139, 16080.
[23]	Xia, G.; Weng, J.; Liu, L.; Verma, P.; Li, Z.; Yu, J.-Q. Nat. Chem. 2019, 11, 571.
[24]	Probst, N.; Grelier, G.; Dahaoui, S.; Alami, M.; Gandon, V.; Messaoudi, S. ACS Catal. 2018, 8, 7781.
[25]	He, G.; Chen, G. Angew. Chem., Int. Ed. 2011, 50, 5192.
[26]	Zhang, Y.-F.; Zhao, H.-W.; Wang, H.; Wei, J.-B.; Shi, Z.-J. Angew. Chem., Int. Ed. 2015, 54, 13686.
[27]	(a) Gandeepan, P.; Ackermann, L. Chem 2018, 4, 199. pmid: 37118417
	(b) Higham, J. I.; Bull, J. A. Org. Biomol. Chem. 2020, 18, 7291. doi: 10.1039/d0ob01587c pmid: 37118417
	(c) Goswami, N.; Bhattacharya, T.; Maiti, D. Nat. Rev. Chem. 2021, 5, 646. doi: 10.1038/s41570-021-00311-3 pmid: 37118417
[28]	Yang, K.; Li, Q.; Liu, Y.; Li, G.; Ge, H. J. Am. Chem. Soc. 2016, 138, 12775. pmid: 27652493
[29]	Li, Y.-H.; Ouyang, Y.; Chekshin, N.; Yu, J.-Q. J. Am. Chem. Soc. 2022, 144, 4727.
[30]	St John-Campbell, S.; White, A. J. P.; Bull, J. A. Org. Lett. 2020, 22, 1807. doi: 10.1021/acs.orglett.0c00124 pmid: 32065758
[31]	Hong, K.; Park, H.; Yu, J.-Q. ACS Catal. 2017, 7, 6938. doi: 10.1021/acscatal.7b02905 pmid: 29038742
[32]	Pan, L.; Yang, K.; Li, G.; Ge, H. Chem. Commun. 2018, 54, 2759.
[33]	Wang, J.; Dong, C.; Wu, L.; Xu, M.; Lin, J.; Wei, K. Adv. Synth. Catal. 2018, 360 3709.
[34]	(a) Dong, C.; Wu, L.; Yao, J.; Wei, K. Org. Lett. 2019, 21, 2085.
	(b) Cheng, Y.; Zheng, J.; Tian, C.; He, Y.; Zhang, C.; Tan, Q.; An, G.; Li, G. Asian J. Org. Chem. 2019, 8, 526.
[35]	Xu, Y.; Young, M. C.; Wang, C.; Magness, D. M.; Dong, G. Angew. Chem., Int. Ed. 2016, 55, 9084.
[36]	Wu, Y.; Chen, Y.-Q.; Liu, T.; Eastgate, M. D.; Yu, J.-Q. J. Am. Chem. Soc. 2016, 138, 14554.
[37]	Yada, A.; Liao, W.; Sato, Y.; Murakami, M. Angew. Chem., Int. Ed. 2017, 56, 1073.
[38]	Shabashov, D.; Daugulis, O. Org. Lett. 2005, 7, 3657. pmid: 16092843
[39]	Le, K. K. A.; Nguyen, H.; Daugulis, O. J. Am. Chem. Soc. 2019, 141, 37, 14728.
[40]	Wasa, M.; Chan, K. S. L.; Zhang, X.-G.; He, J.; Miura, M.; Yu, J.-Q. J. Am. Chem. Soc. 2012, 134, 18570.
[41]	Wu, K.; Lam, N.; Strassfeld, D. A.; Fan, Z.; Qiao, J. X.; Liu, T.; Stamos, D.; Yu, J.-Q. Angew. Chem., Int. Ed. 2024, 63, e202400509.
[42]	(a) Chen, G.; Gong, W.; Zhuang, Z.; Andrä, M. S.; Chen, Y.-Q.; Hong, X.; Yang, Y.-F.; Liu, T.; Houk, K. N.; Yu, J.-Q. Science 2016, 353, 1023.
	(b) Hill, D. E.; Pei, Q.-l.; Zhang, E.-x.; Gage, J. R.; Yu, J.-Q.; Blackmond, D. G. ACS Catal. 2018, 8, 1528.
[43]	Shang, M.; Feu, K. S.; Vantourout, J. C.; Barton, L. M.; Osswald, H. L.; Kato, N.; Gagaring, K.; McNamara, C. W.; Chen, G.; Hu, L.; Ni, S.; Fernández-Canelas, P.; Chen, M.; Merchant, R. R.; Qin, T.; Schreiber, S. L.; Melillo, B.; Yu, J.-Q.; Baran, P. S. Proc. Natl. Acad. Sci. U. S. A. 2019, 116, 8721.
[44]	Andrä, M. S.; Schifferer, L.; Pollok, C. H.; Merten, C.; Gooßen, L. J.; Yu, J.-Q. Chem. Eur. J. 2019, 25, 8503.
[45]	Topczewski, J. J.; Cabrera, P. J.; Saper, N. I.; Sanford, M. S. Nature 2016, 531, 220.
[46]	Cabrera, P. J.; Lee, M.; Sanford, M. S. J. Am. Chem. Soc. 2018, 140, 5599. doi: 10.1021/jacs.8b02142 pmid: 29652497
[47]	Kapoor, M.; Liu, D.; Young, M. C. J. Am. Chem. Soc. 2018, 140, 6818. doi: 10.1021/jacs.8b05061 pmid: 29787251
[48]	(a) Font, M.; Quibell, J. M.; Perry, G. J. P.; Larrosa, I. Chem. Commun. 2017, 53, 5584.
	(b) He, C.; Whitehurst, W. G.; Gaunt, M. J. Chem 2019, 5, 1031.
	(c) He, C.; Zu, B.; Guo, Y.; Ke, J. Synthesis 2021, 53, 2029.
	(d) Das, J.; Mal, D. K.; Maji, S.; Maiti, D. ACS Catal. 2021, 11, 4205.
[49]	Hu, L.; Meng, G.; Yu, J.-Q. J. Am. Chem. Soc. 2022, 144, 20550.
[50]	Yang, J.-M.; Lin, Y.-K.; Sheng, T.; Hu, L.; Cai, X.-P.; Yu, J.-Q. Science 2023, 380, 639.
[51]	Kang, G.; Strassfeld, D. A.; Sheng, T.; Chen, C.-Y.; Yu, J.-Q. Nature 2023, 618, 519.
[52]	Zhang, T.; Zhang, Z.-Y.; Kang, G.; Sheng, T.; Yan, J.-L.; Yang, Y.-B.; Ouyang, Y.; Yu, J.-Q. Science 2024, 384, 793. doi: 10.1126/science.ado1246 pmid: 38753778
[53]	Hoque, M. E.; Yu, J.-Q. Angew. Chem., Int. Ed. 2023, 62, e202312331.
[54]	Strassfeld, D. A.; Chen, C.-Y.; Park, H. S.; Phan, D. Q.; Yu, J.-Q. Nature 2023, 622, 80.
[55]	Chen, K.; Hu, F.; Zhang, S.-Q.; Shi, B.-F. Chem. Sci. 2013, 4, 3906.
[56]	Zhang, S.-Y.; He, G.; Nack, W. A.; Zhao, Y.; Li, Q.; Chen, G. J. Am. Chem. Soc. 2013, 135, 2124.
[57]	Liu, Y.; Yang, K.; Ge, H. Chem. Sci. 2016, 7, 2804.
[58]	Ding, Y.; Han, Y.-Q.; Wu, L.-S.; Zhou, T.; Yao, Q.-J.; Feng, Y.-L.; Li, Y.; Kong, K.-X.; Shi, B.-F. Angew. Chem., Int. Ed. 2020, 59, 14060.
[59]	Liu, Y.; Wang, Y.; Dai, W.; Huang, W.; Li, Y.; Liu, H. Angew. Chem., Int. Ed. 2020, 59, 3491.
[60]	Wu, J.; Kaplaneris, N.; Ni, S.; Kaltenhäuser, F.; Ackermann, L. Chem. Sci. 2020, 11, 6521.
[61]	Gadde, K.; Bheemireddy, N. R.; Heitkämper, J.; Nova, A.; Maes, B. U. W. ACS Catal. 2024, 14, 1157.
[62]	Ano, Y.; Tobisu, M.; Chatani, N. J. Am. Chem. Soc. 2011, 133, 12984.
[63]	Landge, V. G.; Parveen, A.; Nandakumar, A.; Balaraman, E. Chem. Commun. 2018, 54, 7483.
[64]	Han, Y.-Q.; Ding, Y.; Zhou, T.; Yan, S.-Y.; Song, H.; Shi, B.-F. J. Am. Chem. Soc. 2019, 141, 4558.
[65]	Cabrera-Pardo, J. R.; Trowbridge, A.; Nappi, M.; Ozaki, K.; Gaunt, M. J. Angew. Chem., Int. Ed. 2017, 56, 11958.
[66]	Hogg, K. F.; Trowbridge, A.; Alvarez-Pérez, A.; Gaunt, M. J. Chem. Sci. 2017, 8, 8198.
[67]	Desai, L. V.; Hull, K. L.; Sanford, M. S. J. Am. Chem. Soc. 2004, 126, 9542. pmid: 15291549
[68]	Ren, Z.; Mo, F.; Dong, G. J. Am. Chem. Soc. 2012, 134, 16991.
[69]	Chen, K.; Zhang, S.-Q.; Jiang, H.-Z.; Xu, J.-W.; Shi, B.-F. Chem. Eur. J. 2015, 21, 3264.
[70]	Shan, G.; Yang, X.; Zong, Y.; Rao, Y. Angew. Chem., Int. Ed. 2013, 52, 13606.
[71]	Chen, F.-J.; Zhao, S.; Hu, F.; Chen, K.; Zhang, Q.; Zhang, S.-Q.; Shi, B.-F. Chem. Sci. 2013, 4, 4187.
[72]	Bai, H.-Y.; Ma, Z.-G.; Yi, M.; Lin, J.-B.; Zhang, S.-Y. ACS Catal. 2017, 7, 2042.
[73]	Zhu, R.-Y.; Tanaka, K.; Li, G.-C.; He, J.; Fu, H.-Y.; Li, S.-H.; Yu, J.-Q. J. Am. Chem. Soc. 2015, 137, 7067.
[74]	Zhang, Q.; Yin, X.-S.; Chen, K.; Zhang, S.-Q.; Shi, B.-F. J. Am. Chem. Soc. 2015, 137, 8219. doi: 10.1021/jacs.5b03989 pmid: 26067591
[75]	Mao, Y.-J.; Lou, S.-J.; Hao, H.-Y.; Xu, D.-Q. Angew. Chem., Int. Ed. 2018, 57, 14085.
[76]	Chen, Y.-Q.; Singh, S.; Wu, Y.; Wang, Z.; Hao, W.; Verma, P.; Qiao, J. X.; Sunoj, R. B.; Yu, J.-Q. J. Am. Chem. Soc. 2020, 142, 9966.
[77]	He, J.; Shao, Q.; Wu, Q.; Yu, J.-Q. J. Am. Chem. Soc. 2017, 139, 3344.
[78]	Kanyiva, K. S.; Kuninobu, Y.; Kanai, M. Org. Lett. 2014, 16, 1968.
[79]	Pan, J.-L.; Li, Q.-Z.; Zhang, T.-Y.; Hou, S.-H.; Kang, J.-C.; Zhang, S.-Y. Chem. Commun. 2016, 52, 13151.
[80]	Vyhivskyi, O.; Kudashev, A.; Miyakoshi, T.; Baudoin, O. Chem. Eur. J. 2021, 27, 1231;
[81]	Zhang, Z.; Wei, F.; Wang, X.; Zhang, Y.. Org. Lett. 2024, 26, 3586.
[82]	Uttry, A.; Mal, S.; van Gemmeren, M. J. Am. Chem. Soc. 2021, 143, 10895.
[83]	Watanabe, A.; Hama, K.; Watanabe, K.; Fujiwara, Y.; Yokoyama, K.; Murata, S.; Takita, R. Angew. Chem., Int. Ed. 2022, 61, e202202779.
[84]	Wang, X.; Sun, Z.; Li, T.; Perveen, S.; Li, P. Green Chem. 2024, 26, 3767.

钯催化惰性亚甲基C(sp³)—H键分子间官能团化反应

Palladium-Catalyzed Intermolecular Functionalization of Unactivated Methylene C(sp³)—H Bonds

RichHTML

PDF

可视化

摘要/Abstract

引用此文

分享此文

图/表 54

参考文献 84

相关文章 15

编辑推荐

相关统计

本文评价

[1]	姚团利, 王琳琳, 李涛. 钯催化多米诺Heck/分子间偶联反应合成3-烷基取代茚衍生物[J]. 有机化学, 2025, 45(4): 1342-1351.
[2]	区洁晴, 屈培珍, 赵亮. 可见光介导下钯催化脂肪族α-溴代三氟甲基的脱溴还原反应[J]. 有机化学, 2025, 45(4): 1334-1341.
[3]	王曼曼, 习文慧, 吴昊, 白大昌. 过渡金属催化碳氢键活化合成烷基氟烷基化合物的研究进展[J]. 有机化学, 2025, 45(2): 516-530.
[4]	张朝威, 徐兵斌, 刘文龙, 赵敬, 段伟良. 钯催化不对称碳氢键活化合成平面手性二茂铁磺酰胺化合物[J]. 有机化学, 2025, 45(2): 707-716.
[5]	邹瑜, 郭伟聪, 汪君. 不含手性取代基的平面手性环戊二烯基铑催化剂在不对称碳氢键活化中的应用[J]. 有机化学, 2025, 45(2): 466-476.
[6]	杨雪莹, 徐园双, 张新迎, 范学森. 基于2-芳基-3H-吲哚与环丙醇的串联反应合成C2-螺环吲哚啉衍生物[J]. 有机化学, 2025, 45(2): 694-706.
[7]	王晓琴, 许盛, 平媛媛, 孔望清. 光/镍协同催化实现C(sp³)—H键选择性官能团化[J]. 有机化学, 2025, 45(2): 383-422.
[8]	袁晨晖, 焦雷. 手性配体在钯催化配位辅助对映选择性C(sp³)—H键官能团化反应中的应用[J]. 有机化学, 2025, 45(2): 602-619.
[9]	张经明, 何智涛. 过渡金属催化远程二烯的不对称迁移烯丙位碳氢键官能团化[J]. 有机化学, 2025, 45(2): 592-601.
[10]	王凯, 隋佳俊, 龙纯洪, 罗松娟, 钏永明, 秦红波. 基于联苯硼酸的Cochlearol F和Didehydroconicol全合成研究[J]. 有机化学, 2025, 45(1): 343-348.
[11]	杨帆, 范小梦, 姚雪婧, 米瑞杰, 于松杰, 李兴伟, 肖建. 铑(III)催化氧化锍叶立德和重氮化合物环化偶联反应[J]. 有机化学, 2025, 45(1): 331-342.
[12]	刘雯娟, 陈品红. 钯催化1,6-烯炔的环化反应研究[J]. 有机化学, 2024, 44(7): 2077-2091.
[13]	温梦柯, 李宜越, 杜浩康, 陈章培, 杨西发. 铑催化3-芳基-2H-1,4-苯并噁嗪与重氮萘-2H-酮的[3+3]环化合成螺吡喃化合物[J]. 有机化学, 2024, 44(7): 2223-2232.
[14]	张倩, 应垚璐, 张泓银, 徐林博, 林新奎, 黄晓雷. 钯催化SO₂插入的炔丙基乙酸酯和碘代芳烃的还原偶联反应[J]. 有机化学, 2024, 44(6): 2033-2040.
[15]	于蕾, 盛康, 李亭, 唐从辉. 多相铁催化环状醚C(sp³)—H键活化的芳基烯烃氧烷基化[J]. 有机化学, 2024, 44(6): 1978-1986.