Zinc-Mediated C–H Metalations in Modern Organic Synthesis

Daria K. Wanic; Rebecca Melvin; Graeme Barker

doi:10.1055/a-2155-3423

Synthesis, Inhaltsverzeichnis

Synthesis 2023; 55(21): 3487-3501
DOI: 10.1055/a-2155-3423

special topic

C–H Bond Functionalization of Heterocycles

Zinc-Mediated C–H Metalations in Modern Organic Synthesis

Daria K. Wanic

^aInstitute of Chemical Sciences, Heriot-Watt University, Riccarton, Edinburgh, EH14 4AS, UK

,

Rebecca Melvin

^aInstitute of Chemical Sciences, Heriot-Watt University, Riccarton, Edinburgh, EH14 4AS, UK

,

Graeme Barker ∗

^aInstitute of Chemical Sciences, Heriot-Watt University, Riccarton, Edinburgh, EH14 4AS, UK

^bContinuum Flow Lab, Heriot-Watt University, Riccarton, Edinburgh, EH14 4AS, UK

› Institutsangaben

Abstract

Alle Artikel dieser Rubrik

Abstract

C–H Deprotometalations have long occupied a key role in modern organic synthesis in both the research laboratory and pharmaceutical and fine chemical manufacture, thanks to readily accessible reagents and well-established procedures. Typically, organolithiums are the reagent of choice thanks to high reactivity and ease of use but these are incompatible with base- and nucleophile-sensitive functional groups. In comparison, organozinc base complexes offer a milder approach to deprotonative C–H functionalisations, and compatibility with a wide range of functionalities which would be problematic when using the alternative organolithium or organomagnesium reagents has now been demonstrated. Here, we review the current state of the art in zinc-mediated C–H metalations at substituted arenes, heteroarenes, and Csp³–H sites.

1 Introduction

2 Csp²–H Functionalisation Using Zinc Bases

2.1 Functionalised Arenes

2.2 Heterocycles

3 Csp³–H Functionalisation Using Zinc Bases

3.1 Zinc Enolate Formation: Traditional Approach

3.2 Zinc Enolate Formation via Zinc Bases

3.3 Non-Enolic Csp³–H Zincations

4 Conclusion

Key words

metalation - organozinc - C–H functionalisation - deprotonation

Volltext

Referenzen

References
1 Knochel P, Jones P. Organozinc Reagents: A Practical Approach . Oxford University Press; Oxford: 1999
2 Ocampo R, Dolbier WR. Tetrahedron 2004; 60: 9325
3 Elschenbroich C, Salzer A. Organometallics. A Concise Introduction, 2nd ed. Wiley-VCH; Weinheim: 1992
4 Simmons H, Smith R. J. Am. Chem. Soc. 1959; 81: 4256
5 King A, Negishi E, Villani F, Silveira A. J. Org. Chem. 1978; 43: 358
6 Ketels M, Ganiek MA, Weidmann N, Knochel P. Angew. Chem. Int. Ed. 2017; 56: 12770
7 Kondo Y, Shilai M, Uchiyama M, Sakamoto T. J. Am. Chem. Soc. 1999; 121: 3539
8 Clarke AJ, McNamara S, Methcohn O. Tetrahedron Lett. 1974; 15: 2373
9 Wunderlich SH, Knochel P. Angew. Chem. Int. Ed. 2007; 46: 7685
10 Hendrick CE, Bitting KJ, Cho S, Wang Q. J. Am. Chem. Soc. 2017; 139: 11622
11 Hlavinka ML, Hagadorn JR. Organometallics 2007; 26: 4105
12 Micetich RG. Can. J. Chem. 1970; 48: 2006
13 Wong JY. F, Tobin JM, Vilela F, Barker G. Chem. Eur. J. 2019; 25: 12439

14a Neufeld R, Stalke D. Chem. Eur. J. 2016; 22: 12624
14b Armstrong DR, García-Álvarez P, Kennedy AR, Mulvey RE, Parkinson JA. Angew. Chem. Int. Ed. 2010; 49: 3185

15 Mosrin M, Knochel P. Org. Lett. 2009; 11: 1837
16 Balkenhohl M, Jangra H, Makarov IS, Yang SM, Zipse H, Knochel P. Angew. Chem. Int. Ed. 2020; 59: 14992
17 Hlavinka ML, Hagadorn JR. Tetrahedron Lett. 2006; 47: 5049
18 Rees WS, Just O, Schumann H, Weimann R. Polyhedron 1998; 17: 1001
19 Judge NR, Hevia E. Angew. Chem. Int. Ed. 2023; 62: e202303099

20a Kennedy AR, Mulvey RE, Ramsay DL, Robertson SD. Dalton Trans. 2015; 44: 5875
20b Clegg W, Crosbie E, Dale-Black SH, Hevia E, Honeyman GW, Kennedy AR, Mulvey RE, Ramsay DL, Robertson SD. Organometallics 2015; 34: 2580
20c Balloch L, Garden JA, Kennedy AR, Mulvey RE, Rantanen T, Robertson SD, Snieckus V. Angew. Chem. Int. Ed. 2012; 51: 6934
20d Garden JA, Kennedy AR, Mulvey RE, Robertson SD. Chem. Commun. 2012; 48: 5265
20e Mastropierro P, Kennedy AR, Hevia E. Chem. Commun. 2022; 58: 5292
20f Honeyman GW, Armstrong DR, Clegg W, Hevia E, Kennedy AR, McLellan R, Orr SA, Parkinson JA, Ramsay DL, Robertson SD, Towie S, Mulvey RE. Chem. Sci. 2020; 11: 6510
20g Armstrong DR, Baillie SE, Blair VL, Chabloz NG, Diez J, Garcia-Alvarez J, Kennedy AR, Robertson SD, Hevia E. Chem. Sci. 2013; 4: 4259
20h Baillie SE, Blair VL, Blakemore DC, Hay D, Kennedy AR, Pryde DC, Hevia E. Chem. Commun. 2012; 48: 1985
20i Hevia E, Kennedy AR, McCall MD. Dalton Trans. 2012; 41: 98
20j Clegg W, Conway B, Hevia E, McCall MD, Russo L, Mulvey RE. J. Am. Chem. Soc. 2009; 131: 2375
20k Hevia E, Kennedy AR, Klett J, McCall MD. Chem. Commun. 2009; 3240
20l Armstrong DR, García-Álvarez J, Graham DV, Honeyman GW, Hevia E, Kennedy AR, Mulvey RE. Chem. Eur. J. 2009; 15: 3800
20m Francos J, Kennedy AR, O’Hara CT. Dalton Trans. 2016; 45: 6222
20n Balloch L, Kennedy AR, Klett J, Mulvey RE, O’Hara CT. Chem. Commun. 2010; 46: 2319
20o Mastropierro P, Livingstone Z, Robertson SD, Kennedy AR, Hevia E. Organometallics 2020; 39: 4273
20p Armstrong DR, Balloch L, Hevia E, Kennedy AR, Mulvey RE, O'Hara CT, Robertson SD. Beilstein J. Org. Chem. 2011; 7: 1234
20q Blair VL, Blakemore DC, Hay D, Hevia E, Pryde DC. Tetrahedron Lett. 2011; 52: 4590

21a Robertson SD, Uzelac M, Mulvey RE. Chem. Rev. 2019; 119: 8332
21b Borys AM, Dell’Aera M, Capriati V, Hevia E. Adv. Organomet. Chem. 2023; 80: 1

22 Uchiyama M, Miyoshi T, Kajihara Y, Sakamoto T, Otani Y, Ohwada T, Kondo Y. J. Am. Chem. Soc. 2002; 124: 8514
23 Knochel P, Monzon G. Synlett 2010; 304
24 Yoshio H, Takaaki S, Hiroshi K. Chem. Lett. 1983; 12: 1211
25 Bresser T, Mosrin M, Monzon G, Knochel P. J. Org. Chem. 2010; 75: 4686
26 Bresser T, Monzon G, Mosrin M, Knochel P. Org. Process Res. Dev. 2010; 14: 1299
27 Haag B, Mosrin M, Ila H, Malakhov V, Knochel P. Angew. Chem. Int. Ed. 2011; 50: 9794
28 Wunderlich SH, Rohbogner CJ, Unsinn A, Knochel P. Org. Process Res. Dev. 2010; 14: 339
29 Walla P, Kappe CO. Chem. Commun. 2004; 564
30 Wunderlich S, Knochel P. Org. Lett. 2008; 10: 4705
31 Mosrin M, Monzon G, Bresser T, Knochel P. Chem. Commun. 2009; 5615
32 Becker MR, Knochel P. Org. Lett. 2016; 18: 1462
33 Imahori T, Uchiyama M, Sakamoto T, Kondo Y. Chem. Commun. 2001; 2450
34 Effenberger F, Daub W. Chem. Ber. 1991; 124: 2119
35 Connon SJ, Hegarty AF. J. Chem. Soc., Perkin Trans. 1 2000; 1245
36 Taylor RD, MacCoss M, Lawson AD. J. Med. Chem. 2014; 57: 5845
37 Kremsmair A, Sunagatullina AS, Bole LJ, Mastropierro P, Graßl S, Wilke HR, Godineau E, Hevia E, Knochel P. Angew. Chem. Int. Ed. 2022; 61: e202210491
38 Shen K, Fu Y, Li J.-N, Liu L, Guo Q.-X. Tetrahedron 2007; 63: 1568
39 Chevallier F, Mongin F. Chem. Soc. Rev. 2008; 37: 595
40 Meirelles MA, de Toledo I, Thurow S, Barreiro G, Couñago RM, Pilli RA. J. Org. Chem. 2023; 88: 9475
41 Allison BD, Deng X, Li L.-S, Liang J, Mani NS, Ren P, Sales ZS. Org. Process Res. Dev. 2022; 26: 2926
42 Balkenhohl M, Greiner R, Makarov IS, Heinz B, Karaghiosoff K, Zipse H, Knochel P. Chem. Eur. J. 2017; 23: 13046
43 Balkenhohl M, Jangra H, Lenz T, Ebeling M, Zipse H, Karaghiosoff K, Knochel P. Angew. Chem. Int. Ed. 2019; 58: 9244
44 Ziegler DS, Greiner R, Lumpe H, Kqiku L, Karaghiosoff K, Knochel P. Org. Lett. 2017; 19: 5760
45 Balkenhohl M, Salgues B, Hirai T, Karaghiosoff K, Knochel P. Org. Lett. 2018; 20: 3114
46 Schwarzer K, Tullmann CP, Grassl S, Gorski B, Brocklehurst CE, Knochel P. Org. Lett. 2020; 22: 1899
47 Klier L, Ziegler DS, Rahimoff R, Mosrin M, Knochel P. Org. Process Res. Dev. 2017; 21: 660
48 Meyers AI, Collington EW. J. Am. Chem. Soc. 1970; 92: 6676
49 Haas D, Hofmayer MS, Bresser T, Knochel P. Chem. Commun. 2015; 51: 6415
50 Xu Y, Dong G. Chem. Sci. 2018; 9: 1424
51 Lombardo M, Trombini C. The Chemistry of Zinc Enolates . In The Chemistry of Organozinc Compounds . Rappoport Z, Marek I. John Wiley & Sons; Chichester: 2006. 797
52 Diaper DG. M, Kuksis A. Chem. Rev. 1959; 59: 89
53 Gilman H, Speeter M. J. Am. Chem. Soc. 1943; 65: 2255
54 Takai K, Kakiuchi T, Utimoto K. J. Org. Chem. 1994; 59: 2671
55 Gomes P, Gosmini C, Perichon J. Synthesis 2003; 1909
56 Maruoka K, Hashimoto S, Kitagawa Y, Yamamoto H, Nozaki H. Bull. Chem. Soc. Jpn. 1980; 53: 3301
57 Chattopadhyay A, Salaskar A. Synthesis 2000; 561
58 Takahashi T, Nakao N, Koizumi T. Tetrahedron: Asymmetry 1997; 8: 3293
59 Schmittel M, Ghorai MK. Synlett 2001; 1992
60 Seebach D. Angew. Chem. Int. Ed. Engl. 1988; 27: 1624
61 McDonald SL, Wang Q. Chem. Commun. 2014; 50: 2535
62 St John-Campbell S, Sheppard TD. Adv. Synth. Catal. 2022; 364: 2674
63 Dalziel ME, Chen P, Carrera DE, Zhang H, Gosselin F. Org. Lett. 2017; 19: 3446

64a Lovering F, Bikker J, Humblet C. J. Med. Chem. 2009; 52: 6752
64b Lovering F. MedChemComm 2013; 4: 515