Transition-Metal-Catalyzed Direct C–H Functionalization under External-Oxidant-Free Conditions

Jiayu Mo; Lianhui Wang; Yunqi Liu; Xiuling Cui

doi:10.1055/s-0034-1379890

Synthesis, Table of Contents

Synthesis 2015; 47(04): 439-459
DOI: 10.1055/s-0034-1379890

review

Transition-Metal-Catalyzed Direct C–H Functionalization under External-Oxidant-Free Conditions

Jiayu Mo

Key Laboratory of Xiamen Marine and Gene Drugs, Institutes of Molecular Medicine and School of Biomedical Sciences, Huaqiao University & Engineering Research Center of Molecular Medicine, Ministry of Education, Jimei Ave. 668, Xiamen 361021, P. R. of China Email: cuixl@hqu.edu.cn

,

Lianhui Wang

Key Laboratory of Xiamen Marine and Gene Drugs, Institutes of Molecular Medicine and School of Biomedical Sciences, Huaqiao University & Engineering Research Center of Molecular Medicine, Ministry of Education, Jimei Ave. 668, Xiamen 361021, P. R. of China Email: cuixl@hqu.edu.cn

,

Yunqi Liu

Key Laboratory of Xiamen Marine and Gene Drugs, Institutes of Molecular Medicine and School of Biomedical Sciences, Huaqiao University & Engineering Research Center of Molecular Medicine, Ministry of Education, Jimei Ave. 668, Xiamen 361021, P. R. of China Email: cuixl@hqu.edu.cn

,

Xiuling Cui*

Key Laboratory of Xiamen Marine and Gene Drugs, Institutes of Molecular Medicine and School of Biomedical Sciences, Huaqiao University & Engineering Research Center of Molecular Medicine, Ministry of Education, Jimei Ave. 668, Xiamen 361021, P. R. of China Email: cuixl@hqu.edu.cn

› Author Affiliations

Abstract

All articles of this category

Abstract

The use of an ‘internal’ oxidant contained within a directing group has emerged as a practical strategy in metal-catalyzed direct C–H activations in recent years, owing to its being highly sustainable. This review presents the rapid advances of this novel strategy through analyzing and comparing the different types of internal oxidant in transition-metal-catalyzed C–H activation reactions.

1 Introduction

2 The N–O Bond as Internal Oxidant

2.1 The O-Linked Moiety as Leaving Group

2.1.1 N-Oxide

2.1.2 N-Acyloxy

2.1.3 Oxime

2.1.4 N-Methoxy or N-Hydroxy

2.1.5 N-Pivaloyloxy or O-tert-Butyloxycarbonyloxy

2.1.6 Miscellaneous

2.2 The N-Linked Moiety as Leaving Group

3 The N–N Bond as Internal Oxidant

4 The N–S Bond as Internal Oxidant

5 The S–Cl Bond as Internal Oxidant

5 The Si–H Bond as Internal Oxidant

6 Conclusion

Key words

internal oxidant - transition-metal catalysis - C–H activation - redox-neutral process - green chemistry

Full Text

References

References

1a Chen DY.-K, Youn SW. Chem. Eur. J. 2012; 18: 9452
1b Gutekunst WR, Baran PS. Chem. Soc. Rev. 2011; 40: 1976
1c McMurray L, O’Hara F, Gaunt MJ. Chem. Soc. Rev. 2011; 40: 1885

2a Ackermann L. Acc. Chem. Res. 2014; 47: 281
2b Engle KM, Yu J.-Q. J. Org. Chem. 2013; 78: 8927
2c Mousseau JJ, Charrette AB. Acc. Chem. Res. 2013; 46: 412
2d Kuhl N, Hopkinson MN, Wencel-Delord J, Glorius F. Angew. Chem. Int. Ed. 2012; 51: 10236
2e Wang Y, Cheng G, Cui X. Chin. J. Org. Chem. 2012; 32: 2018
2f Yeung CS, Dong VM. Chem. Rev. 2011; 111: 1215
2g Colby DA, Bergman RG, Ellman JA. Chem. Rev. 2010; 110: 624
2h Ackermann L. Chem. Rev. 2011; 111: 1315
2i Mkhalid IA. I, Barnard JH, Marder TB, Murphy JM, Hartwig JF. Chem. Rev. 2010; 110: 890
2j Sehnal P, Taylor RJ. K, Fairlamb IJ. S. Chem. Rev. 2010; 110: 824
2k Willis MC. Chem. Rev. 2010; 110: 725
2l Dobereiner GE, Crabtree RH. Chem. Rev. 2010; 110: 681
2m Thansandote P, Lautens M. Chem. Eur. J. 2009; 15: 5874
2n Ackermann L, Vicente R, Kapdi AR. Angew. Chem. Int. Ed. 2009; 48: 9792
2o Campeau L.-C, Stuart DR, Fagnou K. Aldrichimica Acta 2007; 40: 35
2p Alberico D, Scott ME, Lautens M. Chem. Rev. 2007; 107: 174
2q Bergman RG. Nature 2007; 446: 391
2r Godula K, Sames D. Science 2006; 312: 67; and references cited therein

3a Patureau FW, Glorius F. Angew. Chem. Int. Ed. 2011; 50: 1977

For reviews related with internal oxidant, see:

3b Li B, Dixneuf PH. Chem. Soc. Rev. 2013; 42: 5744
3c Arockiam PB, Bruneau C, Dixneuf PH. Chem. Rev. 2012; 112: 5879
3d Zhu C, Wang R, Falck JR. Chem. Asian J. 2012; 7: 1502
3e Song G, Wang F, Li X. Chem. Soc. Rev. 2012; 41: 3651
3f Patureau FW, Wencel-Delord J, Glorius F. Aldrichimica Acta 2012; 45: 31
3g Satoh T, Miura M. Chem. Eur. J. 2010; 16: 11212

4a Ackermann L, Beck EM, Bouffard J, Daugulis O, Davies HM. L, Dick AR, Bois JD, Fagnou K, Gaunt MJ, Itami K, Larock RC, Lautens M, Li C.-J, Liu G, Mariampillai B, Martins A, Shi F, Vicente R, Wu Y, Xia J.-B, Yoo W.-J, You S.-L, Zalatan DN. Top. Curr. Chem. 2012; 292: 35
4b Kanyiva KS, Nakao Y, Hiyama T. Angew. Chem. Int. Ed. 2007; 46: 8872
4c Cho SH, Hwang SJ, Chang S. J. Am. Chem. Soc. 2008; 130: 9254

5 Wu J, Cui X, Chen L, Jiang G, Wu Y. J. Am. Chem. Soc. 2009; 131: 13888
6 Huang X, Huang J, Du C, Zhang X, Song F, You J. Angew. Chem. Int. Ed. 2013; 52: 12970
7 Tan Y, Hartwig JF. J. Am. Chem. Soc. 2010; 132: 3676

8a Díaz-Requejo MM, Belderrain TR, Nicasio MC, Trofimenko S, Pérez PJ. J. Am. Chem. Soc. 2003; 125: 12078
8b Thu H.-Y, Yu W.-Y, Che C.-M. J. Am. Chem. Soc. 2006; 128: 9048
8c Li Z, Capretto DA, Rahaman RO, He C. J. Am. Chem. Soc. 2007; 129: 12058
8d Stokes BJ, Dong H, Leslie BE, Pumphrey AL, Driver TG. J. Am. Chem. Soc. 2007; 129: 7500
8e Chiba S, Hattori G, Narasaka K. Chem. Lett. 2007; 36: 52

9a Tsang WC. P, Zheng N, Buchwald SL. J. Am. Chem. Soc. 2005; 127: 14560
9b Chen X, Hao X.-S, Goodhue CE, Yu J.-Q. J. Am. Chem. Soc. 2006; 128: 6790
9c Inamoto K, Saito T, Katsuno M, Sakamoto T, Hiroya K. Org. Lett. 2007; 9: 2931
9d Yamamoto M, Matsubara S. Chem. Lett. 2007; 36: 172
9e Jordan-Hore JA, Johansson CC. C, Gulias M, Beck EM, Gaunt MJ. J. Am. Chem. Soc. 2008; 130: 16184
9f Tsang WC. P, Munday RH, Brasche G, Zheng N, Buchwald SL. J. Org. Chem. 2008; 73: 7603
9g Brasche G, Buchwald SL. Angew. Chem. Int. Ed. 2008; 47: 1932
9h Mei T.-S, Wang X, Yu J.-Q. J. Am. Chem. Soc. 2009; 131: 10806

10 Too PC, Wang Y.-F, Chiba S. Org. Lett. 2010; 12: 5688
11 Too PC, Chua SH, Wong SH, Chiba S. J. Org. Chem. 2011; 76: 6159

12a Parthasarathy K, Cheng C.-H. J. Org. Chem. 2009; 74: 9359

For similar reactions, see:

12b Martin RM, Bergman RG, Ellman JA. J. Org. Chem. 2012; 77: 2501
12c Parthasarathy K, Jeganmohan M, Cheng C.-H. Org. Lett. 2008; 10: 325

13a Zhang X, Chen D, Zhao M, Zhao J, Jia A, Li X. Adv. Synth. Catal. 2011; 353: 719

The transformation was also acheived by ruthenium catalysis; for related reports, see:

13b Kornhaaß C, Li J, Ackermann L. J. Org. Chem. 2012; 77: 9190
13c Chinnagolla RK, Pimparkar S, Jeganmohan M. Org. Lett. 2012; 14: 3032

14a Too PC, Noji T, Lim YJ, Li X, Chiba S. Synlett 2011; 2789

For a similar transformation, see:

14b Hyster TK, Rovis T. Chem. Commun. 2011; 47: 11846

15 Zheng L, Ju J, Bin Y, Hua R. J. Org. Chem. 2012; 77: 5794
16 Rakshit S, Grohmann C, Besset T, Glorius F. J. Am. Chem. Soc. 2011; 133: 2350
17 Li B, Ma J, Wang N, Feng H, Xu S, Wang B. Org. Lett. 2012; 14: 736
18 Wasa M, Yu J.-Q. J. Am. Chem. Soc. 2008; 130: 14058
19 Guimond N, Gouliaras C, Fagnou K. J. Am. Chem. Soc. 2010; 132: 6908
20 Li B, Feng H, Xu S, Wang B. Chem. Eur. J. 2011; 17: 12573

21a Ackermann L, Fenner S. Org. Lett. 2011; 13: 6548
21b Kornhaaß C, Kuper C, Ackermann L. Adv. Synth. Catal. 2014; 356: 1619

22a Guimond N, Gorelsky SI, Fagnou K. J. Am. Chem. Soc. 2011; 133: 6449

For similar transformations, see:

22b Zhao D, Lied F, Glorius F. Chem. Sci. 2014; 5: 2869
22c Yu D.-G, de Azambuja F, Gensch T, Daniliuc CG, Glorius F. Angew. Chem. Int. Ed. 2014; 53: 9650
22d Shi Z, Boultadakis-Arapinis M, Koester DC, Glorius F. Chem. Commun. 2014; 50: 2650

23 Xu L, Zhu Q, Huang G, Cheng B, Xia Y. J. Org. Chem. 2012; 77: 3017
24 Hyster TK, Knörr L, Ward TR, Rovis T. Science 2012; 338: 500
25 Ye B, Cramer N. Science 2012; 338: 504
26 Wang H, Grohmann C, Nimphius C, Glorius F. J. Am. Chem. Soc. 2012; 134: 19592

27a Primas N, Bouillon A, Rault S. Tetrahedron 2010; 66: 8121
27b Tyrrell E, Brookes P. Synthesis 2004; 469

28 Wang H, Glorius F. Angew. Chem. Int. Ed. 2012; 51: 7318

29a Zeni G, Larock RC. Chem. Rev. 2006; 106: 4644
29b Yamauchi M, Morimoto M, Miura T, Murakami M. J. Am. Chem. Soc. 2010; 132: 54
29c Miura T, Yamauchi M, Kosaka A, Murakami M. Angew. Chem. Int. Ed. 2010; 49: 4955
29d Ochi Y, Kurahashi T, Matsubara S. Org. Lett. 2011; 13: 1374
29e Tran DN, Cramer N. Angew. Chem. Int. Ed. 2010; 49: 8181
29f Larock RC, Berrios-Peña NG, Fried CA. J. Org. Chem. 1991; 56: 2651

30 Huckins JR, Bercot EA, Thiel OR, Hwang T.-L, Bio MM. J. Am. Chem. Soc. 2013; 135: 14492
31 Cui S, Zhang Y, Wu Q. Chem. Sci. 2013; 4: 3421
32 Neely JM, Rovis T. J. Am. Chem. Soc. 2013; 135: 66
33 Xu X, Liu Y, Park C.-M. Angew. Chem. Int. Ed. 2012; 51: 9372
34 Ng K.-H, Chan AS. C, Yu W.-Y. J. Am. Chem. Soc. 2010; 132: 12862

35a Feng C, Feng D, Loh T.-P. Org. Lett. 2013; 15: 3670

With respect to organic alcohols further C–H functionalization that involve C–H/C–O cleavages, see:

35b Muto K, Yamaguchi J, Itami K. J. Am. Chem. Soc. 2012; 134: 169
35c Xu H, Muto K, Yamaguchi J, Zhao C, Itami K, Musaev DG. J. Am. Chem. Soc. 2014; 136: 14834
35d Ackermann L, Fenner S. Chem. Commun. 2011; 47: 430
35e Oi S, Funayama R, Hattori T, Inoue Y. Tetrahedron 2008; 64: 6051
35f Ackermann L, Vicente R, Althammer A. Org. Lett. 2008; 10: 2299
35g So CM, Lau CP, Kwong FY. Chem. Eur. J. 2011; 17: 761
35h Ackermann L, Althammer A, Fenner S. Angew. Chem. Int. Ed. 2009; 48: 201
35i Ackermann L, Althammer A, Born R. Angew. Chem. Int. Ed. 2006; 45: 2619
35j Ackermann L, Pospech J, Potukuchi HK. Org. Lett. 2012; 14: 2146

36 Liu G, Shen Y, Zhou Z, Lu X. Angew. Chem. Int. Ed. 2013; 52: 6033
37 Shen Y, Liu G, Zhou Z, Lu X. Org. Lett. 2013; 15: 3366
38 Li XG, Liu K, Zou G, Liu PN. Adv. Synth. Catal. 2014; 356: 1496
39 Liu B, Song C, Sun C, Zhou S, Zhu J. J. Am. Chem. Soc. 2013; 135: 16625
40 Wang C, Huang Y. Org. Lett. 2013; 15: 5294
41 Zhao D, Shi Z, Glorius F. Angew. Chem. Int. Ed. 2013; 52: 12426
42 Zheng L, Hua R. Chem. Eur. J. 2014; 20: 2352
43 Chuang S.-C, Gandeepan P, Cheng C.-H. Org. Lett. 2013; 15: 5750
44 Zhang Q.-R, Huang J.-R, Zhang W, Dong L. Org. Lett. 2014; 16: 1684

45a Wu Z, Song H, Cui X, Pi C, Du W, Wu Y. Org. Lett. 2013; 15: 1270

For a similar example of C–H functionalizations through S–Cl bond cleavage, see:

45b Saidi O, Marafie J, Ledger AE. W, Liu PM, Mahon MF, Kociok-Köhn G, Whittlesey MK, Frost CG. J. Am. Chem. Soc. 2011; 133: 19298

46a Tsukada N, Hartwig JF. J. Am. Chem. Soc. 2005; 127: 5022

For a similar transformation, see:

46b Cheng C, Simmons EM, Hartwig JF. Angew. Chem. Int. Ed. 2013; 52: 8984

47a Kuznetsov A, Gevorgyan V. Org. Lett. 2012; 14: 914

For a similar transformation, see:

47b Kuznetsov A, Onishi Y, Inamoto Y, Gevorgyan V. Org. Lett. 2013; 15: 2498

48 Ureshino T, Yoshida T, Kuninobu Y, Takai K. J. Am. Chem. Soc. 2010; 132: 14324
49 Kuninobu Y, Yamauchi K, Tamura N, Seiki T, Takai K. Angew. Chem. Int. Ed. 2013; 52: 1520
50 Kuninobu Y, Nakahara T, Takeshima H, Takai K. Org. Lett. 2013; 15: 426