C–H Bond Functionalization & Synthesis in the 21st Century: A Brief History and Prospectus

M. Christina White

doi:10.1055/s-0032-1317701

Synlett, Inhaltsverzeichnis

Synlett 2012; 23(19): 2746-2748
DOI: 10.1055/s-0032-1317701

cluster

C–H Bond Functionalization & Synthesis in the 21^st Century: A Brief History and Prospectus

M. Christina White

Roger Adams Laboratory, Department of Chemistry, University of Illinois, Urbana, IL 61801, USA Fax: +1(217)2445943 eMail: white@scs.uiuc.edu

› Institutsangaben

Abstract

Alle Artikel dieser Rubrik

Abstract

Among the frontier challenges facing synthetic chemistry in the 21st century are the interconnected goals of increasing control of chemical reactivity and synthesizing complex molecules with higher levels of efficiency. Catalytic C–H bond functionalization reactions are increasingly being discovered that meet the criterion for useful reactivity (i.e. preparative, predictably selective, and general). Consequently, such reactions are enabling chemists to exploit strategies for complex molecule synthesis and derivatization previously accessible only in nature. This preface highlights some of the achievements and important challenges that remain in the area of C–H bond functionalization.�

Key words

C–H activation - site-selective oxidation - bio-inspired methods - synthetic efficiency - complex molecule synthesis

Volltext

Referenzen

References and Notes
1 Groves JT, Nemo TE, Myers RS. J. Am. Chem. Soc. 1979; 101: 1032 , and references therein

2a Bennett MA, Milner DL. J. Am. Chem. Soc. 1969; 91: 6983
2b Gol’dshleger NF, Es’kova VV, Shilov AE, Shteinman AA. Zh. Fiz. Khim. (Engl. Transl.) 1972; 46: 785
2c Komiya S, Ito T, Cowie M, Yamamoto A, Ibers JA. J. Am. Chem., Soc. 1976; 98: 3874
2d Crabtree RH, Mihelcic JM, Quirk JM. J. Am. Chem. Soc. 1979; 101: 7738

For mechanistic studies, see:

2e Bengali AA, Schultz RH, Moore B, Bergman RG. J. Am. Chem. Soc. 1994; 116: 9585
2f Stahl SS, Labinger JA, Bercaw JE. Angew. Chem. Int. Ed. 1998; 37: 2180

3 Murai S, Kakiuchi F, Sekine S, Tanaka Y, Kamatani A, Sonoda M, Chatani N. Nature 1993; 366: 529

4a Dick AR, Hull KL, Sanford MS. J. Am. Chem. Soc. 2004; 126: 2300
4b Chen X, Goodhue CE, Yu J.-Q. J. Am. Chem. Soc. 2006; 128: 12634
4c Hull KL, Anani WQ, Sanford MS. J. Am. Chem. Soc. 2006; 128: 7134
4d Campeau L.-C, Parisien M, Jean A, Fagnou K. J. Am. Chem. Soc. 2006; 128: 581
4e Chiong HA, Pham Q.-N, Daugulis O. J. Am. Chem. Soc. 2007; 129: 9879
4f Jordon-Hore JA, Johansson CC. C, Gulias M, Beck EM, Gaunt MJ. J. Am. Chem. Soc. 2008; 130: 16184
4g Wang C, Piel I, Glorius F. J. Am. Chem. Soc. 2009; 131: 4194
4h Wang X, Truesdale L, Yu J.-Q. J. Am. Chem. Soc. 2010; 132: 3648

For an example with rhodium, see:

4i Thalji RK, Ahrendt KA, Bergman RG, Ellman JA. J. Am. Chem. Soc. 2001; 123: 9692

5a Breslow R, Gellman SH. J. Am. Chem. Soc. 1983; 105: 6729
5b Doyle MP, Dyatkin AB, Roos GH.P, Canas F, Pierson DA, van Basten A. J. Am. Chem. Soc. 1994; 116: 4507
5c Taber DF, Ruckle Jr. RE. J. Am. Chem. Soc. 1986; 108: 7686

6a Espino CG, Du Bois J. Modern Rhodium-Catalyzed Organic Reactions. Wiley-VCH; Weinheim: 2005
6b Davies HM. L, Beckwith RE. J. Chem. Rev. 2003; 103: 2861

7a Groves JT, Neumann R. J. Am. Chem. Soc. 1989; 111: 2900
7b Breslow R, Huang Y, Zhang X, Yang J. Proc. Nat. Acad. Sci. 1997; 94: 11156
7c Das S, Incarvito CD, Crabtree RH, Brudvig GW. Science 2006; 213: 1941

8 For a general carboxylic acid group directed approach to C–H hydroxylations with a non-heme iron oxo, see: Bigi MA, Reed SA, White MC. J. Am. Chem. Soc. 2012; 134: 9721

9a Cho J.-Y, Tse MK, Holmes D, Maleczka Jr. RE, Smith III. MR. Science 2002; 295: 305
9b Ishiyaya T, Takagi J, Ishida K, Miyaura N, Anasrasi NR, Hartwig JF. J. Am. Chem. Soc. 2002; 124: 390

For C–H esterification, see:

10a Chen MS, White MC. J. Am. Chem. Soc. 2004; 126: 1346
10b Chen MS, Prabagaran N, Labenz NA, White MC. J. Am. Chem. Soc. 2005; 127: 6970
10c Fraunhoffer KJ, Prabagaran N, Sirois LE, White MC. J. Am. Chem. Soc. 2006; 128: 9032
10d Delcamp JH, Brucks AP, White MC. J. Am. Chem. Soc. 2008; 130: 11270
10e Vermeulen NA, Delcamp JH, White MC. J. Am. Chem. Soc. 2010; 132: 11323
10f Gormisky PE, White MC. J. Am. Chem. Soc. 2011; 133: 12584
10g Mitsudome T, Umetani T, Nosaka N, Mori K, Mizugaki T, Ebitani K, Kaneda K. Angew. Chem. Int. Ed. 2006; 45: 481
10h Pilarski LT, Selander N, Bose D, Szabo KJ. Org. Lett. 2009; 11: 5518
10i Lin B.-L, Labinger JA, Bercaw JE. Can. J. Chem. 2009; 87: 264
10j Thiery E, Aouf C, Belloy J, Harakat D, Le Bras J, Muzart J. J. Org. Chem. 2010; 75: 1771
10k Henderson WH, Check CT, Proust N, Stambuli JP. Org. Lett. 2010; 12: 824
10l Campbell AN, White PB, Guzei IA, Stahl SS. J. Am. Chem. Soc. 2010; 132: 15116

For C–H amination, see:

11a Larock RC, Hightower TR, Hasvold LA, Peterson KP. J. Org. Chem. 1996; 61: 3584
11b Fraunhoffer KJ, White MC. J. Am. Chem. Soc. 2007; 129: 7274
11c Reed SA, White MC. J. Am. Chem. Soc. 2008; 130: 3316
11d Liu G, Yin G, Wu L. Angew. Chem. Int. Ed. 2008; 47: 4733
11e Rice GT, White MC. J. Am. Chem. Soc. 2009; 131: 11707
11f Reed SA, Mazzotti AR, White MC. J. Am. Chem. Soc. 2009; 131: 11701
11g Qi X, Rice GT, Lall MS, Plummer MS, White MC. Tetrahedron 2010; 66: 4816
11h Nahra F, Liron F, Prestat G, Mealli C, Messaoudi A, Poli G. Chem. Eur. J. 2009; 15: 11078
11i Shimizu Y, Obora Y, Ishii Y. Org. Lett. 2010; 12: 1372

For C–H alkylation, see:

12a Young AJ, White MC. J. Am. Chem. Soc. 2008; 130: 14090
12b Young AJ, White MC. Angew. Chem. Int. Ed. 2011; 50: 6824
12c Lin S, Song C.-X, Cai G.-X, Wang W.-H, Shi Z.-J. J. Am. Chem. Soc. 2008; 130: 12901

13 For dehydrogenations, see: Stang EM, White MC. J. Am. Chem. Soc. 2011; 133: 14892

14a Bergman RG. Nature 2007; 446: 391
14b Godula K, Sames D. Science 2006; 312: 67

15 Chen MS, White MC. Science 2007; 318: 783
16 Chen MS, White MC. Science 2010; 327: 566
17 White MC. Science 2012; 335: 807

18a Liu W, Groves JT. J. Am. Chem. Soc. 2010; 132: 12847
18b Liu W, Cheng M.-J, Nielsen RJ, Goddard III. WA, Groves JT. Science 2012; 337: 1322
18c Litvinas ND, Brodsky BH, Du Bois J. Angew. Chem. Int. Ed. 2009; 48: 4513

19 Paradine SM, White MC. J. Am. Chem. Soc. 2012; 134: 2036

For examples of late-state C–H oxidations:

20a Fraunhoffer KJ, Bachovchin DA, White MC. Org. Lett. 2005; 7: 223
20b Covell DJ, Vermeulen NA, Labenz NA, White MC. Angew. Chem. Int. Ed. 2006; 45: 8217
20c Stang EM, White MC. Nature Chem. 2009; 1: 547
20d Stang EM, White MC. Angew. Chem. Int. Ed. 2011; 50: 2094
20e Hinmann A, Du Bois J. J. Am. Chem. Soc. 2003; 125: 11510
20f Davies HM. L, Dai X, Long MS. J. Am. Chem. Soc. 2006; 128: 2485
20g Kim J, Ashenhurst JA, Movassaghi M. Science 2009; 324: 238

For seminal examples using allylic C–H oxidation, see:

20h Nicolaou KC, Yang Z, Liu JJ, Ueno H, Nantermet PG, Gui RK, Claibaurne CF, Reynaud J, Couladouros EA, Paulvannan K, Sorenson EJ. Nature 1994; 367: 630
20i Wender PA, Jesudason CD, Nakhira H, Tamura N, Tebe AL, Ueno YJ. J. Am. Chem. Soc. 1997; 119: 12976

21a Bigi MA, Reed SA, White MC. Nature Chem. 2011; 3: 216
21b ref. 8, 15, 16.
21c Wender PA, Hilinski MK, Mayweg AV.W. Org. Lett. 2005; 7: 79