Transition-Metal-Catalyzed Alkenyl sp2 C–H Activation: A Short Account

Manikantha Maraswami; Teck-Peng Loh

doi:10.1055/s-0037-1611649

Synthesis, Table of Contents

CC BY-ND-NC 4.0 · Synthesis 2019; 51(05): 1049-1062
DOI: 10.1055/s-0037-1611649

short review

Copyright with the author

Transition-Metal-Catalyzed Alkenyl sp² C–H Activation: A Short Account

Manikantha Maraswami

^aDivision of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University, Singapore 637616, Singapore Email: teckpeng@ntu.edu.sg

,

Teck-Peng Loh *

^aDivision of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University, Singapore 637616, Singapore Email: teckpeng@ntu.edu.sg

^bInstitute of Advanced Synthesis, Jiangsu National Synergetic Innovation Center for Advanced Materials, Nanjing Tech University, Nanjing, Jiangsu 210009, P. R. of China

^cHefei National Laboratory for Physical Sciences at the Microscale, iChEM (Collaborative Innovation Center of Chemistry for Energy Materials), University of Science and Technology of China, Hefei, Anhui 230026, P. R. of China

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Abstract

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Published as part of the 50 Years SYNTHESIS – Golden Anniversary Issue

Abstract

Alkenes are ubiquitous in Nature and their functionalization continues to attract attention from the scientific community. On the other hand, activation of alkenyl sp² C–H bonds is challenging due to their chemical properties. In this short account, we elucidate, discuss and describe the utilization of transition-metal catalysts in alkene activation and provide useful strategies to synthesize organic building blocks in an efficient and sustainable manner.

1 Introduction

2 Breakthrough

3 Controlling E/Z, Z/E Selectivity

3.1 Esters and Amides as Directing Groups

3.2 The Chelation versus Non-Chelation Concept

4 Other Alkene Derivatives

5 Intramolecular C–H Activation

6 Conclusion and Future Projects

Key words

transition metals - enamides - acrylamides - macrocycles - acrylates - alkenylation - alkynylation

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References

References

1a Fringuelli F, Taticchi A. Dienes in the Diels-Alder Reaction . Wiley-Interscience; New York: 1990
1b Luh T.-Y, Wong K.-T. Synthesis 1993; 349
1c Mehta G, Rao HS. P. In The Chemistry of Dienes and Polyenes, Vol. 1. Rappoport Z. John Wiley & Sons; New York: 1997: 359
1d Negishi E.-I, Huang Z, Wang G, Mohan S, Wang C, Hattori H. Acc. Chem. Res. 2008; 41: 14741
1e Negishi E.-I. Angew. Chem. Int. Ed. 2011; 50: 6738
1f Keller-Schierlein W, Meyer M, Cellai L, Cerrini S, Lamba D, Segre A, Fedeli W, Brufani M. J. Antibiot. 1984; 37: 1357
1g Kuttruff CA, Geiger S, Cakmak M, Mayer P, Trauner D. Org. Lett. 2012; 14: 1070

2a Santos L, Fant F, Medeiros MA, Borremans FA. M, Costa MC, Curto MJ. M. Magn. Reson. Chem. 2000; 38: 937
2b Carter KD, Panek JS. Org. Lett. 2004; 6: 55
2c Tanaka J, Higa T. Tetrahedron Lett. 1996; 37: 5535
2d Cutignano A, Bruno I, Bifulco G, Casapullo A, Debitus C, Gomez-Paloma L, Riccio R. Eur. J. Org. Chem. 2001; 775

For selected very recent reviews on transition-metal-catalyzed C–H activation, see:

3a Mishra NK, Sharma S, Park J, Han S, Kim IS. ACS Catal. 2017; 7: 2821
3b Hirano K, Miura M. Chem. Sci. 2018; 9: 22
3c Song GY, Li XW. Acc. Chem. Res. 2015; 48: 1007
3d Gensch T, Hopkinson MN, Glorius F, Wencel-Delord J. Chem. Soc. Rev. 2016; 45: 2900
3e Ping L, Chung DS, Bouffard J, Lee SG. Chem. Soc. Rev. 2017; 46: 4299
3f Leitch JA, Bhonoah Y, Frost CG. ACS Catal. 2017; 7: 5618
3g Wang S, Chen SY, Yu XQ. Chem. Commun. 2017; 53: 3165 ; and the references cited therein

4a Tokuyama H, Yokoshima S, Yamashita T, Fukuyama T. Tetrahedron Lett. 1998; 39: 3189
4b Hatanaka Y, Hiyama T. J. Org. Chem. 1988; 53: 918
4c Miyaura N, Suzuki A. J. Chem. Soc., Chem. Commun. 1979; 866
4d King AO, Okukado N, Negishi EI. J. Chem. Soc., Chem. Commun. 1977; 683
4e Sonogashira K, Tohda Y, Hagihara N. Tetrahedron Lett. 1975; 4467
4f Heck RF, Nolley JP. J. Org. Chem. 1972; 37: 2320
4g Tamao K, Sumitani K, Kumada M. J. Am. Chem. Soc. 1972; 94: 4374

5a da Silva MJ, Gusevskaya EV. J. Mol. Catal. A: Chem. 2001; 176: 23
5b da Silva MJ, Goncalves JA, Alves RB, Howarth OW, Gusevskaya EV. J. Organomet. Chem. 2004; 689: 302

6 Hatamoto Y, Sakaguchi S, Ishii Y. Org. Lett. 2004; 6: 4623
7 Xu YH, Lu J, Loh TP. J. Am. Chem. Soc. 2009; 131: 1372
8 Xu YH, Wang WJ, Wen ZK, Hartley JJ, Loh TP. Tetrahedron Lett. 2010; 51: 3504
9 Yu HF, Jin WW, Sun CL, Chen JP, Du WM, He SB, Yu ZK. Angew. Chem. Int. Ed. 2010; 49: 5792
10 Zhang YX, Cui ZL, Li ZJ, Liu ZQ. Org. Lett. 2012; 14: 1838
11 Zhang X, Wang M, Zhang MX, Xu YH, Loh TP. Org. Lett. 2013; 15: 5531
12 Besset T, Kuhl N, Patureau FW, Glorius F. Chem. Eur. J. 2011; 17: 7167
13 Zhang J, Loh TP. Chem. Commun. 2012; 48: 11232

14a The Chemistry of Dienes and Polyenes . Rappoport Z. John Wiley & Sons; New York: 1997
14b Yet L. Chem. Rev. 2003; 103: 4283
14c Matsumoto A, Odani T, Sada K, Miyata M, Tashiro K. Nature 2000; 405: 328

15a Engle KM, Mei T.-S, Wasa M, Yu J.-Q. Acc. Chem. Res. 2012; 45: 788
15b De Sarkar S, Liu W, Kozhushkov SI, Ackermann L. Adv. Synth. Catal. 2014; 356: 1461

16a Sonoda M, Kakiuchi F, Kamatani A, Chatani N, Murai S. Chem. Lett. 1996; 109
16b Park SH, Kim JY, Chang S. Org. Lett. 2011; 13: 2372
16c Graczyk K, Ma WB, Ackermann L. Org. Lett. 2012; 14: 4110
16d Padala K, Pimparkar S, Madasamy P, Jeganmohan M. Chem. Commun. 2012; 48: 7140

17 Hu XH, Zhang J, Yang XF, Xu YH, Loh TP. J. Am. Chem. Soc. 2015; 137: 3169
18 Feng C, Feng DM, Loh TP. Chem. Commun. 2015; 51: 342

19a Chinchilla R, Nájera C. Chem. Rev. 2014; 114: 1783
19b Meretina IA, Ionin BI, Tebby JC. Alkynes in Cycloadditions . Wiley-Blackwell; New Jersey: 2013
19c Negishi E, Anastasia L. Chem. Rev. 2003; 103: 1979
19d Tykwinski RR. Angew. Chem. Int. Ed. 2003; 42: 1566
19e Diederich F, Stang PJ, Tykwinski RR. Acetylene Chemistry: Chemistry, Biology and Material Science . Wiley-VCH; Weinheim: 2005
19f Brand JP, Waser J. Chem. Soc. Rev. 2012; 41: 4165

20 Kolb HC, Finn MG, Sharpless KB. Angew. Chem. Int. Ed. 2001; 40: 2004

21a Kong J.-R, Ngai M.-Y, Krische MJ. J. Am. Chem. Soc. 2006; 128: 718
21b Lumbroso A, Cooke ML, Breit B. Angew. Chem. Int. Ed. 2013; 52: 1890
21c Li H, Walsh PJ. J. Am. Chem. Soc. 2005; 127: 8355
21d Lloyd Jones GC. Org. Biomol. Chem. 2003; 1: 215
21e Trost BM, Toste FD, Pinkerton AB. Chem. Rev. 2001; 101: 2067
21f Diver ST, Giessert AJ. Chem. Rev. 2004; 104: 1317
21g Zhang L, Sun J, Kozmin SA. Adv. Synth. Catal. 2006; 348: 2271
21h Aubert C, Buisine O, Malacria M. Chem. Rev. 2002; 102: 813
21i Zeng X. Chem. Rev. 2013; 113: 6864
21j Fairlamb IJ. S. Angew. Chem. Int. Ed. 2004; 43: 1048
21k Miller KM, Luanphaisarnnont T, Molinaro C, Jamison TK. J. Am. Chem. Soc. 2004; 126: 4130
21l Mamane V, Hannen P, Fürstner A. Chem. Eur. J. 2004; 10: 4556

22a Zein N, Sinba AM, McGahren WJ, Ellestad GA. Science 1988; 240: 1198
22b Ratovelomanana V, Linstrumelle G. Synth. Commun. 1981; 11: 917
22c Nicolaou KC, Dai MW. Angew. Chem. Int. Ed. 1991; 30: 1387
22d El-Jaber N, Estevez-Braun A, Ravelo AG, Munoz-Munoz O, Rodriguez-Afonso A, Murguia JR. J. Nat. Prod. 2003; 66: 722
22e Fontana A, d’Ippolito G, D’Souza L, Mollo E, Parameswaram PS, Cimino G. J. Nat. Prod. 2001; 64: 131
22f Gung BW, Kumi G. J. Org. Chem. 2004; 69: 348

23 Collins KD, Lied F, Glorius F. Chem. Commun. 2014; 50: 4459
24 Feng C, Feng DM, Luo Y, Loh TP. Org. Lett. 2014; 16: 5956
25 Kuhl N, Schroder N, Glorius F. Org. Lett. 2013; 15: 3860
26 Wang HG, Beiring B, Yu DG, Collins KD, Glorius F. Angew. Chem. Int. Ed. 2013; 52: 12430
27 Lu P, Feng C, Loh T.-P. Org. Lett. 2015; 17: 3210

28a Mishra NK, Park J, Sharma S, Han S, Kim M, Shin Y, Jang JB, Kwak JH, Jung YH, Kim IS. Chem. Commun. 2014; 50: 2350
28b Guo L, Chen YY, Zhang R, Peng QJ, Xu LT, Pan XH. Chem. Asian J. 2017; 12: 289
28c Xu LT, Zhang C, He YP, Tan LS, Ma DW. Angew. Chem. Int. Ed. 2016; 55: 321
28d Zhou Q, Zhang JF, Cao H, Zhong R, Hou XF. J. Org. Chem. 2016; 81: 12169
28e Zhang XS, Zhu QL, Zhang YF, Li YB, Shi ZJ. Chem. Eur. J. 2013; 19: 11898

29a Manikandan R, Madasamy P, Jeganmohan M. ACS Catal. 2016; 6: 230
29b Jin HM, Zhu ZB, Jin N, Xie J, Cheng YX, Zhu CJ. Org. Chem. Front. 2015; 2: 378
29c Cai SJ, Lin SY, Yi XL, Xi CJ. J. Org. Chem. 2017; 82: 512
29d Li J, Ackermann L. Org. Chem. Front. 2015; 2: 1035

30a Brook AG, Quigley MA, Peddle GJ. D, Schwartz NV, Warner CM. J. Am. Chem. Soc. 1960; 82: 5102
30b Yoshida J, Itoh M, Matsunaga S, Isoe S. J. Org. Chem. 1992; 57: 4877

31 Song SJ, Lu P, Liu H, Cai SH, Feng C, Loh TP. Org. Lett. 2017; 19: 2869

For selected reviews on trifluoromethylations, see:

32a Merino E, Nevado C. Chem. Soc. Rev. 2014; 43: 6598
32b Charpentier J, Fruh N, Togni A. Chem. Rev. 2015; 115: 650
32c Liu X, Xu C, Wang M, Liu Q. Chem. Rev. 2015; 115: 683
32d Yang XY, Wu T, Phipps RJ, Toste FD. Chem. Rev. 2015; 115: 826
32e Alonso C, de Marigorta EM, Rubiales G, Palacios F. Chem. Rev. 2015; 115: 1847

33 Feng C, Loh TP. Angew. Chem. Int. Ed. 2013; 52: 12414

34a Muller K, Faeh C, Diederich F. Science 2007; 317: 1881
34b Hagmann WK. J. Med. Chem. 2008; 51: 4359
34c Kirsch P. Modern Fluoroorganic Chemistry: Synthesis Reactivity, Applications. Wiley-VCH; Weinheim: 2004
34d Purser S, Moore PR, Swallow S, Gouverneur V. Chem. Soc. Rev. 2008; 37: 320
34e Uneyama K. Organofluorine Chemistry . Blackwell; Oxford: 2006

35 Wen ZK, Xu YH, Loh TP. Chem. Eur. J. 2012; 18: 13284

36a Wang C, Ge HB. Chem. Eur. J. 2011; 17: 14371
36b Shang R, Ilies L, Asako S, Nakamura E. J. Am. Chem. Soc. 2014; 136: 14349
36c Le Bras J, Muzart J. Chem. Rev. 2011; 111: 1170
36d Kozhushkov SI, Ackermann L. Chem. Sci. 2013; 4: 886
36e Cho SH, Kim JY, Kwak J, Chang S. Chem. Soc. Rev. 2011; 40: 5068

37a Shi BF, Maugel N, Zhang YH, Yu JQ. Angew. Chem. Int. Ed. 2008; 47: 4882
37b Paquette LA, Lobben PC. J. Org. Chem. 1998; 63: 5604
37c Nerzstormes M, Thornton ER. J. Org. Chem. 1991; 56: 2489
37d Engle KM, Yu JQ. J. Org. Chem. 2013; 78: 8927

38 Liang QJ, Yang C, Meng FF, Jiang B, Xu YH, Loh TP. Angew. Chem. Int. Ed. 2017; 56: 5091
39 Zhou H, Chung WJ, Xu YH, Loh TP. Chem. Commun. 2009; 3472

40a Zhang L, Wu J. J. Am. Chem. Soc. 2008; 130: 12250
40b Denmark SE, Sweis RF. Acc. Chem. Res. 2002; 35: 835

41 Zhou H, Xu YH, Chung WJ, Loh TP. Angew. Chem. Int. Ed. 2009; 48: 5355
42 Xu YH, Chok YK, Loh TP. Chem. Sci. 2011; 2: 1822
43 Pankajakshan S, Xu YH, Cheng JK, Low MT, Loh TP. Angew. Chem. Int. Ed. 2012; 51: 5701
44 Boultadakis-Arapinis M, Hopkinson MN, Glorius F. Org. Lett. 2014; 16: 1630
45 Feng C, Feng DM, Loh TP. Chem. Commun. 2014; 50: 9865
46 Feng C, Loh TP. Chem. Sci. 2012; 3: 3458
47 Xu YH, Zhang QC, He T, Meng FF, Loh TP. Adv. Synth. Catal. 2014; 356: 1539
48 Xu YH, He T, Zhang QC, Loh TP. Chem. Commun. 2014; 50: 2784
49 Hu XH, Yang XF, Loh TP. Angew. Chem. Int. Ed. 2015; 54: 15535

Selected reviews and examples of metal-catalyzed cross-couplings of enol phosphates:

50a You W, Li Y, Brown MK. Org. Lett. 2013; 15: 1610
50b Hansen AL, Ebran J.-P, Ahlquist M, Norrby P.-O, Skrydstrup T. Angew. Chem. Int. Ed. 2006; 45: 3349
50c Fuwa H. Synlett 2011; 6

For recent reviews, see:

51a Gigant N, Chausset-Boissarie L, Gillaizeau I. Chem. Eur. J. 2014; 20: 548
51b Matsubara R, Kobayashi S. Acc. Chem. Res. 2008; 41: 292

52 Ding R, Huang ZD, Liu ZL, Wang TX, Xu YH, Loh TP. Chem. Commun. 2016; 52: 5617
53 Jiang B, Meng FF, Liang QJ, Xu YH, Loh TP. Org. Lett. 2017; 19: 914

54a Mayer AM. S, Rodriguez AD, Berlinck RG. S, Hamann MT. Biochim. Biophys. Acta, Gen. Subj. 2009; 1790: 283
54b Coleman JJ, Ghosh S, Okoli I, Mylonakis E. PLoS One 2011; 6: 25321
54c Yu X, Sun D. Molecules 2013; 18: 6230
54d Jelić D, Antolović R. Antibiotics 2016; 5: 29

55 Jiang B, Zhao M, Li SS, Xu YH, Loh TP. Angew. Chem. Int. Ed. 2018; 57: 555