过渡金属催化的碳氢活化是方法学研究的热门领域。近些年，通过引入辅助基团作为导向基对化合物进行C—H键功能化，吸引了研究者们极大的关注。借助导向基，不仅可以大大提高反应的区域和立体选择性，更能提高催化反应的效率。本文综述了近三年内，通过羧基、吡啶等含氮、氧等导向基团进行导向基辅助的碳氢键活化，构建C—C键、C—O键以及C—N键的方法，重点讨论了催化剂的选择和反应机理的研究，同时也总结了目前所存在的问题和局限性，并对今后的发展方向作了展望。
Transition-metal-catalyzed C—H bond activation is currently one of the most extensively studied research topics in organic synthesis. Recently, the directing group assisted C—H functionlization has drawn more attention from the researchers. The directing groups could enhance the reactive speed, selectivity and catalysis efficiency, which usually contain the nitrogen or oxygen atom. The review aims to summarize the methods of construction of C-C bond, C-O bond or C—N bond by C—H bond activation via introducing a directing group, including carboxyl, pyridnyl groups and so on during the past 3 years. The reaction mechanisms, the existing problems and limitations of this field are also included in this review. Finally, the development trend of this area is prospected.
Contents
1 Introduction
2 Recent advances in directing group C—H activation
2.1 Nitrogen-containing groups as the directing group
2.2 Oxygen-containing groups as the directing group
3 Conclusion
[1] a) Qin Y, Zhu L H, Luo S Z. Chem. Rev., 2017, 117:9433; b) Wei Y, Hu P, Zhang M, Su W P. Chem. Rev., 2017, 117:8864
[2] Kawasaki Y, Ishikawa Y, Igawa K, Tomooka K. J. Am. Chem. Soc., 2011, 133:20712
[3] Wang P, Verma P, Xia G, Shi J, Qiao J X, Tao S, Cheng P T W, Poss M A, Farmer M E, Yeung K S, Yu J Q. Nature, 2017, 551:489.
[4] Wu X F, Anbrarasan P, Neumannr H, Beller M. Angew. Chem. Int. Ed., 2010, 49:7316.
[5] Arockiam P B, Bruneau C, Dixneuf P H. Chem. Rev., 2012, 112:5879.
[6] Satoh T, Kawamura Y, Miura M, Nomura M. Angew. Chem. Int. Ed., 1997, 36:1740.
[7] a) Mei T S, Giri R, Maugel N, Yu J Q. Angew. Chem. Int. Ed., 2008, 47:5215; b) Chen X, Hao X S, Goodhue C E, Yu J Q. J. Am. Chem. Soc., 2006, 128:6790.
[8] Tang C H, Jiao N. J. Am. Chem. Soc., 2012, 134:18924.
[9] Fang H, Dou Y D, Ge J Y, Chhabra M, Sun H, Zhang P, Zheng Y G, Zhu Q. J. Org. Chem., 2017, 82:11212.
[10] a) Halima T B, Vandavasi J K, Shkoor M, Newman S G. ACS Catal., 2017, 7:2176; b) Wang J Q, He J, Zhi C, Luo B, Li X M, Pan Y, Cao X Q, Gu H W. RSC Adv., 2014, 4:16607.
[11] a) Xie F, Qi Z S, Li X W. Angew. Chem. Int. Ed., 2013, 52:11862; b) Saidi O, Marafie J, Ledger A E W, Liu P M, Mahon M F, Kohn G K, Whittlesey M K, Frost C G. J. Am. Chem. Soc. 2011, 133:19298; c) Stowers K J, Sanford M S. Org. Lett., 2009, 11:4584.
[12] Lou S J, Chen Q, Wang Y F, Xu D Q, Du X H, He J Q, Mao Y J, Xu Z Y. ACS Catal., 2015, 5:2846.
[13] Wang Z, Kuninobu Y, Kanai M. J. Am. Chem. Soc., 2015, 137:6140.
[14] Pawar G G, Brahmanandan A, Kapur M. Org. Lett., 2016, 18:448.
[15] Ravi M, Allu S, Swamy K C K. J. Org. Chem., 2017, 82:2355.
[16] Xu Y W, Zhou X K, Zheng G F, Li X W. Org. Lett., 2017, 19, 5256.
[17] Zhang G F, Li Y, Xie X Q, Ding C R. Org. Lett., 2017, 19:1216.
[18] McAteer D C, Javed E, Huo L, Huo S. Org. Lett., 2017, 19:1606.
[19] a) Liu B X, Li B, Wang B Q. Chem. Commun., 2015, 51:16334; b) Wang X, Qiu R H, Yan C Y, Reddy V P, Zhu L Z, Xu X H, Yin S F. Org. Lett., 2015, 17:1970; c) Yan S B, Zhang S, Duan W L. Org. Lett., 2015, 17:2458; d) Yan Q Q, Chen Z K, Yu W L, Yin H, Liu Z X, Zhang Y H. Org. Lett., 2015, 17:2482.
[20] Seuss A M, Ertem M Z, Cramer C J, Stahl S S. J. Am. Chem. Soc., 2013, 135:9797.
[21] Qiao H, Sun S Y, Yang F, Zhu Y, Zhu W G, Dong Y, Wu Y S, Kong X T, Jiang L, Wu Y J. Org. Lett., 2015, 17:6086.
[22] Wei J, Jiang J X, Xiao X S, Lin D E, Deng Y F, Ke Z F, Jiang W, Zeng W. J. Org. Chem., 2016, 81:946.
[23] Liu X G, Xu J, Shen C, Zhu X L, Zhang P F, Ajitha M J, Huang K W, An Z F. Chem. Asian J., 2016, 11:882.
[24] Wang Z, Kuninobu Y, Kanai M. Org. Lett., 2014, 16:4790.
[25] Tan Z, Zhu G G. Chem. Commoun., 2016, 52:6845.
[26] Takamatsu D, Hirano K, Miura M. Org. Lett., 2015, 17:4066.
[27] Dou Y D, Xie Z D, Sun Z G, Fang H L, Shen C, Zhang P F, Zhu Q. ChemCatChem., 2016, 8:3570.
[28] Lang K, Davis L, Wallace S, Mahesh M, Cox D J, Blackman M L, Fox J M, Chin J W. J. Am. Chem. Soc., 2012, 134:10317.
[29] Lemieux G A, Graffenried C L, Bertozzi C R. J. Am. Chem. Soc., 2003, 125:4708.
[30] Testa C, Gigot E, Genc S, Decrau R, Roger J, Hierso J. Angew. Chem., 2016, 128:5645.
[31] Mboyi C D, Testa C, Reeb S, Genc S, Cattey H, Lessard P F, Roger J, Hierso J C. ACS Catal., 2017, 7:8493.
[32] Peng Z H, Yu Z, Li T, Li N, Wang Y L, Song L H, Jiang C Y. Organometallics., 2017, 36:2826.
[33] a) Krajcovicova S, Soural M. ACS Comb. Sci., 2016, 18:371; b) Zhou L H, Zhang H W, Tao S J, Ehteshami M, Cho J H, McBrayer T R, Tharnish P, Whitaker T, Amblard F, Coats S J, Schinaz R F, ACS Med. Chem. Lett., 2016, 7:17; c) Keough D T, Adams T S, Jones M K, Brereton M, Guddat L W, Jersey J, J. Med. Chem., 2006, 49:7479.
[34] Guo H M, Jiang L L, Niu H Y, Rao W H, Liang L, Mao R Z, Li D Y, Qu G R. Org. Lett., 2011, 13:2008.
[35] Kim H J, Ajitha M J, Lee Y, Ryu J, Kim J, Lee Y, Jung Y, Chang S. J. Am. Chem. Soc., 2014, 136:1132.
[36] Yu M Y, Wang Z Q, Tian M, Lu C H, Li S L, Du H G. J. Org. Chem., 2016, 81:3435.
[37] Ruan Z, Lackner S, Ackermann L. ACS Catal., 2016, 6:4690.
[38] Warratz S, Burns D J, Zhu C, Korvorapun K, Rogge T, Scholz J, Jooss C, Gelman D, Ackermann L. Angew. Chem. Int. Ed., 2017, 56:1557.
[39] Bettadapur K R, Lanke V, Ramaiah P K. Org. Lett. 2015, 17:4658.
[40] Potter T J, Kamber D N, Mercado B Q, Ellman J A. ACS Catal., 2017, 7:150.
[41] Xu J C, Liu Y, Wang Y, Li Y J, Xu X H, Jin Z. Org. Lett., 2017, 19:1562.
[42] Hoque M E, Bisht R, Haldar C, Chattopadhyay B. J. Am. Chem. Soc., 2017, 139:7745.
[43] Sato T, Yoshida T, Mamari H H A, Ilies L, Nakamura E. Org. Lett., 2017, 19:5458.
[44] Cheng H C, Hernandez J G, Bolm C. Org. Lett., 2017, 19:6284.
[45] a) Miao J M, Yang K, Kurek M, Ge H B. Org. Lett., 2015, 17:3738; b)He J, Takise R, Fu H Y, Yu J Q. J. Am. Chem. Soc., 2015, 137:4618.
[46] Zhu R Y, Denis T G S, Shao Y, He J, Sieber J D, Senanayake C H, Yu J Q. J. Am. Chem. Soc., 2017, 139:5724.
[47] Zhu C L, Zhang Y F, Kan J, Zhao H Q, Su W P. Org. Lett., 2015, 17:3418.
[48] Biafora A, Krause T, Hackenberger D, Belitz F, Goossen L J, Angew. Chem. Int. Ed., 2016, 55:14752.
[49] Mei R, Zhang S K, Ackermann L. Org. Lett., 2017, 19:3171.
[50] Mandal A, Dana S, Sahoo H, Sankar G, Baidya G M. Org. Lett., 2017, 19:2430.
[51] Aman A, Wulff W D. Synthesis, 2010, 21:3670.
[52] Zhao Y T, Huang B B, Yang C, Li B, Gou B Q, Xia W J. ACS Catal., 2017, 7:2446.
[53] Tan E, Konovalov A I, Fernandez G A, Dorel R, Echavarren A M. Org. Lett., 2017, 19:5561
[54] a) Putro W S, Kojima T, Hara T, Ichikuni N, Shimazu S. Catal. Sci. Technol., 2017, 7:3637; b) Yu H, Ru S, Dai G Y, Zhai Y Y, Lin H L, Han S, Wei Y G. Angew. Chem. Int. Ed., 2017, 56:3867.
[55] Bisht R, Chattopadhyay B. J. Am. Chem. Soc., 2016, 138:84.
[56] Zhang F L, Hong K, Li T J, Park H, Yu J Q. Science, 2016, 351:252.
[57] Liu X H, Park H, Hu J H, Hu Y, Zhang Q L, Wang B L, Sun B, Yeung K S, Zhang F L, Yu J Q. J. Am. Chem. Soc., 2017, 139:888.
[58] Ma F, Lei M, Hu L H. Org. Lett., 2016, 18:2708.
[59] Yang F Z, Rauch K, Kettelhoit K, Ackermann L. Angew. Chem. Int. Ed., 2014, 53:11285.
[60] Chen X Y, Ozturk S, Sorensen E J. Org. Lett., 2017, 19:6280.
[61] Yang K, Li Q, Liu Y B, Li G G, Ge H B. J. Am. Chem. Soc., 2016, 138:12775.
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