Trifluoromethylated Internal Alkynes: Versatile Building Blocks for the ­Preparation of Various Fluorine-Containing Molecules

Tsutomu Konno

doi:10.1055/s-0033-1340867

Synlett, Table of Contents

Synlett 2014; 25(10): 1350-1370
DOI: 10.1055/s-0033-1340867

account

Trifluoromethylated Internal Alkynes: Versatile Building Blocks for the Preparation of Various Fluorine-Containing Molecules

Tsutomu Konno*

Department of Chemistry and Materials Technology, Kyoto Institute of Technology Matsugasaki, Sakyo-ku, Kyoto 606-8585, Japan Fax: +81(75)7247517 Email: konno@kit.ac.jp

› Author Affiliations

Abstract

All articles of this category

Abstract

Trifluoromethylated alkynes (CF₃ alkynes) are among the most powerful synthetic intermediates for the preparation of fluorine-containing materials. In this account, our recent advances on the synthesis and reactions of trifluoromethylated alkynes are described.

1 Introduction

2 Synthesis of Trifluoromethylated Alkynes

3 Addition Reactions of H–M, C–M and M–M (M = Metal) with Trifluoromethylated Alkynes

3.1 Hydrostannation (H–Sn)

3.2 Hydroboration (H–B)

3.3 Hydrosilylation (H–Si)

3.4 Other Hydrometallations (H–Cu, H–Al)

3.5 Carbostannylation (C–Sn)

3.6 Carbocupration (C–Cu)

3.7 Carbopalladation (C–Pd)

3.8 Bisstannylation (Sn–Sn)

3.9 Silylstannylation (Si–Sn)

4 Cyclization Using Trifluoromethylated Alkynes

4.1 Synthesis of Trifluoromethylated Dihydroisoxazoles

4.2 Synthesis of Trifluoromethylated Indoles

4.3 Synthesis of Trifluoromethylated Benzofurans

4.4 Synthesis of Trifluoromethylated Isoquinolines

4.5 Synthesis of Trifluoromethylated Cyclopentenones

4.6 Synthesis of Trifluoromethylated Benzenes

5 Concluding Remarks

Key words

trifluoromethylated alkynes - regioselectivity - stereoselectivity - hydrometallation - carbometallation - bismetallation - cyclization

Full Text

References

References

For reviews, see:

1a Purser S, Moore PR, Swallow S, Gouverneur V. Chem. Soc. Rev. 2008; 37: 320
1b Müller K, Faeh C, Diederich F. Science 2007; 317: 1881
1c Isanbor C, O’Hagan D. J. Fluorine Chem. 2006; 127: 303
1d Kirk KL. J. Fluorine Chem. 2006; 127: 1013
1e Bégué J.-P, Bonnet-Delpon D. J. Fluorine Chem. 2006; 127: 992
1f Paulini R, Müller K, Diederich F. Angew. Chem. Int. Ed. 2005; 44: 1788
1g Zanda M. New J. Chem. 2004; 28: 1401

2a Nie J, Guo H.-C, Cahard D, Ma J.-A. Chem. Rev. 2011; 111: 455
2b Valero G, Companyó X, Rios R. Chem. Eur. J. 2011; 17: 2018
2c Qiu X.-L, Qing F.-L. Eur. J. Org. Chem. 2011; 3261
2d Shimizu M, Hiyama T. Angew. Chem. Int. Ed. 2005; 44: 214
2e Mikami K, Itoh Y, Yamanaka M. Chem. Rev. 2004; 104: 1
2f Lin P, Jiang J. Tetrahedron 2000; 56: 3635
2g Singh RP, Shreeve JM. Tetrahedron 2000; 56: 7613

For reports on the preparation of CF₃ alkynes published prior to 2000, see:

3a Yamanaka H, Mantani T, Shiomi K, Ishihara T. Chem. Lett. 1998; 615
3b Yamazaki T, Mizutani K, Kitazume T. J. Org. Chem. 1995; 60: 6046
3c Yamazaki T, Mizutani K, Kitazume T. J. Chem. Soc., Chem. Commun. 1995; 51
3d Umemoto T, Ishihara S. J. Am. Chem. Soc. 1993; 115: 2156
3e Hamper BC. Org. Synth. 1991; 70: 246
3f Laurent AJ, Le Drean IM, Selmi A. Tetrahedron Lett. 1991; 26: 3071
3g Meazza G, Capuzzi L, Piccardi P. Synthesis 1989; 331
3h Bunch JE, Bumgardner CL. J. Fluorine Chem. 1987; 36: 313
3i Baum K, Bedford CD, Hunadi RJ. J. Org. Chem. 1982; 47: 2251
3j Calas P, Moreau P, Commeyras A. J. Chem. Soc., Chem. Commun. 1982; 433
3k Kobayashi Y, Yamashita T, Takahashi K, Kuroda H, Kumadaki I. Tetrahedron Lett. 1982; 23: 343
3l Finnegan WG, Norris WP. J. Org. Chem. 1963; 28: 1139

4 Hiyama T, Sato K, Fujita M. Bull. Chem. Soc. Jpn. 1989; 62: 1352
5 Yoneda N, Matsuoka S, Miyaura N, Fukuhara T, Suzuki A. Bull. Chem. Soc. Jpn. 1990; 63: 2124

6a Hiyama T, Sato K. Synlett 1990; 53
6b Kuwabara M, Fukunishi K, Nomura M, Yamanaka H. J. Fluorine Chem. 1988; 41: 227
6c Kuwabara M, Murakami A, Fukunishi K, Nomura M, Yamanaka H. J. Fluorine Chem. 1989; 42: 105

7a Xu T, Liu G. Org. Lett. 2012; 14: 5416
7b Hanamoto T, Hakoshima Y, Egashira M. Tetrahedron Lett. 2004; 45: 7573
7c Porta PL, Capuzzai L, Bettarini F. Synthesis 1994; 287
7d Meazza G, Zanardi G. J. Fluorine Chem. 1991; 55: 199

8a Zhang X.-G, Chen M.-W, Zhong P, Hu M.-H. J. Fluorine Chem. 2008; 129: 335
8b Prié G, Thibonnet J, Abarbri M, Duchêne A, Parrain J.-L. Synlett 1998; 839
8c Qing F.-L, Zhang Y. Tetrahedron Lett. 1997; 38: 6729
8d Henne AL, Nager M. J. Am. Chem. Soc. 1952; 74: 650

9a Prié G, Richard S, Parrain J.-L, Duchêne A, Abarbri M. J. Fluorine Chem. 2002; 117: 35
9b Cen W, Ni Y, Shen Y. J. Fluorine Chem. 1995; 73: 161

10a Tamura K, Ishihara T, Yamanaka H. J. Fluorine Chem. 1994; 68: 25
10b Yamanaka H, Tamura K, Funabiki K, Fukunishi K, Ishihara T. J. Fluorine Chem. 1992; 57: 177
10c Funabiki K, Tamura K, Ishihara T, Yamanaka H. Bull. Chem. Soc. Jpn. 1994; 67: 3021
10d Allen AD, Angelini G, Paradisi C. Tetrahedron Lett. 1989; 30: 1315

For reports on the preparation of CF₃ alkynes published since 2000, see:

11a Iqbal N, Jung J, Park S, Cho EJ. Angew. Chem. Int. Ed. 2014; 53: 539
11b Wang X, Lin J, Zhang C, Xiao J, Zheng X. Chin. J. Chem. 2013; 31: 915
11c Presset M, Oehlrich D, Rombouts F, Molander GA. J. Org. Chem. 2013; 78: 12837
11d Zheng H, Huang Y, Wang Z, Li H, Huang K.-W, Yuan Y, Weng Z. Tetrahedron Lett. 2012; 53: 6646
11e Jiang X, Chu L, Qing F.-L. J. Org. Chem. 2012; 77: 1251
11f Luo D.-F, Xu J, Fu Y, Guo Q.-X. Tetrahedron Lett. 2012; 53: 2769
11g Weng Z, Li H, He W, Yao L.-F, Tan J, Chen J, Yuan Y, Huang K.-W. Tetrahedron 2012; 68: 2527
11h Zhang K, Qiu X.-L, Huang Y, Qing F.-L. Eur. J. Org. Chem. 2012; 58
11i Senecal TD, Parsons AT, Buchwald SL. J. Org. Chem. 2011; 76: 1174
11j Urban C, Cadoret F, Blazejewski J.-C, Magnier E. Eur. J. Org. Chem. 2011; 4862
11k Chu L, Qing F.-L. J. Am. Chem. Soc. 2010; 30: 3229
11l Chu L, Qing F.-L. Org. Lett. 2010; 12: 5060
11m Chu L, Qing F.-L. J. Am. Chem. Soc. 2010; 132: 7262
11n Chen X.-Y, Qiu X.-L, Qing F.-L. Tetrahedron 2008; 64: 2310
11o Ishihara T, Mantani T, Konno T, Yamanaka H. Tetrahedron 2006; 62: 3783
11p Brisdon AK, Crossley IR. Chem. Commun. 2002; 2420

For other synthetic applications of CF₃ alkynes, see:

12a Duda B, Tverdomed S, Röschenthaler G.-V. J. Fluorine Chem. 2013; 152: 29
12b Alkhafaji HM. H, Ryabukhin DS, Muzalevskiy VM, Vasilyev AV, Fukin GK, Shastin AV, Nenajdenko VG. Eur. J. Org. Chem. 2013; 1132
12c Matsumoto A, Ilies L, Nakamura E. J. Am. Chem. Soc. 2011; 133: 6557
12d Aikawa K, Hioki Y, Shimizu N, Mikami K. J. Am. Chem. Soc. 2011; 133: 20092
12e Katagiri T, Nakanishi H, Ohno K, Seiki T, Isobe T, Kataoka K, Uneyama K. Tetrahedron 2011; 67: 3041
12f Kawatsura M, Namioka J, Kajita K, Yamamoto M, Tsuji H, Itoh T. Org. Lett. 2011; 13: 3285
12g Lumbroso A, Vautravers NR, Breit B. Org. Lett. 2010; 12: 5498
12h Hanamoto T, Yamada K. J. Org. Chem. 2009; 74: 7559
12i Shimizu M, Higashi M, Takeda Y, Jiang G, Murai M, Hiyama T. Synlett 2007; 1163
12j Konno T, Ishihara T In Fluorine-Containing Synthons . Solochonok VA. American Chemical Society; Washington DC: 2005. Chap. 9, 190-203
12k Labrosse J.-R, Lhoste P, Sinou D. J. Org. Chem. 2001; 66: 6634

13 Konno T, Chae J, Kanda M, Nagai G, Tamura K, Ishihara T, Yamanaka H. Tetrahedron 2003; 59: 7571
14 Yamanaka H, Araki T, Kuwabara M, Fukunishi K, Nomura M. Nippon Kagaku Kaishi 1986; 1321
15 Jennings MP, Cork EA, Ramachandran V. J. Org. Chem. 2000; 65: 8763
16 Konno T, Nagai G, Ishihara T. J. Fluorine Chem. 2006; 127: 510

17a Konno T, Moriyasu K, Ishihara T. Synthesis 2009; 1087

It has been reported that various CF₃ propargylamines can be prepared through the reaction of a CF₃ acetylide with N-sulfinylimines, see:

17b Chen X.-Y, Qiu X.-L, Qing F.-L. Tetrahedron 2008; 64: 2301
17c Chen Q, Qiu X.-L, Qing F.-L. J. Fluorine Chem. 2007; 128: 1182

18 Konno T, Kishi M, Ishihara T. Beilstein J. Org. Chem. 2012; 8: 2207

19a Konno T, Chae J, Tanaka T, Ishihara T, Yamanaka H. J. Fluorine Chem. 2006; 127: 36
19b Chae J, Konno T, Kanda M, Ishihara T, Yamanaka H. J. Fluorine Chem. 2003; 120: 185

20 Konno T, Kishi M, Ishihara T, Yamada S. Tetrahedron 2012; 70: 2455
21 Konno T, Chae J, Tanaka T, Ishihara T, Yamanaka H. Chem. Commun. 2004; 690
22 Konno T, Taku K, Yamada S, Moriyasu K, Ishihara T. Org. Biomol. Chem. 2009; 7: 1167

23a Konno T, Takehana T, Chae J, Ishihara T, Yamanaka H. J. Org. Chem. 2004; 69: 2188

For palladium-catalyzed carbostannylation reactions, see:

23b Shimizu M, Jiang G, Murai M, Takeda Y, Nakao Y, Hiyama T, Shirakawa E. Chem. Lett. 2005; 1700
23c Shirakawa E, Yoshida H, Nakao Y, Hiyama T. Org. Lett. 2000; 2: 2209

24a Konno T, Morigaki A, Ninomiya K, Miyabe T, Ishihara T. Synthesis 2008; 564
24b Konno T, Daitoh T, Noiri A, Chae J, Ishihara T, Yamanaka H. Tetrahedron 2005; 61: 9391
24c Konno T, Daitoh T, Noiri A, Chae J, Ishihara T, Yamanaka H. Org. Lett. 2004; 6: 933

25 Shimizu and Hiyama also developed an efficient approach to panomifene around the same time, see: Liu X, Shimizu M, Hiyama T. Angew. Chem. Int. Ed. 2004; 43: 879
26 Konno T, Taku K, Ishihara T. J. Fluorine Chem. 2006; 127: 966
27 Our methodology has been applied for the synthesis of a CF3-containing estrogen-receptor modulator, see: Smith ND, Kahraman M, Govek SP, Nagasawa JJ, Lai AG. Brit. UK Patent 2483736, 2012
28 Konno T, Kinugawa R, Morigaki A, Ishihara T. J. Org. Chem. 2009; 74: 8456
29 Apte S, Radetich B, Shin S, RajanBabu TV. Org. Lett. 2004; 6: 4053 ; and references cited therein
30 Konno T, Kinugawa R, Ishihara T, Yamada S. Org. Biomol. Chem. 2014; 12: 1611

31a Konno T, Chae J, Ishihara T, Yamanaka H. J. Org. Chem. 2004; 69: 8258
31b Chae J, Konno T, Ishihara T, Yamanaka H. Chem. Lett. 2004; 33: 314

It has been reported that a π-allylpalladium complex having a CF₃ group at the terminal carbon is attacked exclusively by nucleophiles at the carbon distal to a CF₃ group, see:

32a Okano T, Matsubara H, Kusukawa T, Fujita M. J. Organomet. Chem. 2003; 676: 43
32b Konno T, Nagata K, Ishihara T, Yamanaka H. J. Org. Chem. 2002; 67: 1768
32c Konno T, Ishihara T, Yamanaka H. Tetrahedron Lett. 2000; 41: 8467
32d Hanzawa Y, Ishizawa S, Ito H, Kobayashi Y, Taguchi T. J. Chem. Soc., Chem. Commun. 1990; 394
32e Hanzawa Y, Ishizawa S, Kobayashi Y. Chem. Pharm. Bull. 1988; 36: 4209

More recently, the reaction in which nucleophilic displacement of a CF₃-containing π-allylpalladium complex with nitrogen nucleophiles occurs at the carbon attached to a CF₃ group was reported, see:

32f Hirakawa T, Kawatsura M, Itoh T. J. Fluorine Chem. 2013; 152: 62
32g Hirakawa T, Ikeda K, Ikeda D, Tanaka T, Ogasa H, Kawatsura M, Itoh T. Tetrahedron 2011; 43: 8238

33 Jiang Z.-X, Qing F.-L. J. Fluorine Chem. 2003; 123: 57
34 Konno T, Chae J, Ishihara T, Yamanaka H. Tetrahedron 2004; 60: 11695

35a Larock RC, Yum EK, Refvik MD. J. Org. Chem. 1998; 63: 7652
35b Larock RC, Yum EK, Doty MJ, Sham KK. C. J. Org. Chem. 1995; 60: 3270

The addition reaction of phenol or thiophenol toward CF₃ alkynes has been reported, see:

36a Bumgardner CL, Bunch JE, Whangbo M.-H. J. Org. Chem. 1986; 51: 4083
36b Bunch JE, Whangbo M.-H. Tetrahedron Lett. 1986; 27: 1883

37 Konno T, Chae J, Miyabe T, Ishihara T. J. Org. Chem. 2005; 70: 10172
38 Kizirian J.-C, Aiguabella N, Pesquer A, Fustero S, Bello P, Verdaguer X, Riera A. Org. Lett. 2010; 12: 5620
39 Konno T, Kida T, Tani A, Ishihara T. J. Fluorine Chem. 2012; 144: 147
40 Aiguabella N, del Pozo C, Verdaguer X, Fustero S, Riera A. Angew. Chem. Int. Ed. 2013; 52: 5355

41a Müller C, Lachicotte RJ, Jones WD. Organometallics 2002; 21: 1975

For pioneering work, see:

41b Garcia JJ, Sierra C, Torrens H. Tetrahedron Lett. 1996; 37: 6097

42a Konno T, Moriyasu K, Kinugawa R, Ishihara T. Org. Biomol. Chem. 2010; 8: 1718

A highly regioselective trimerization of CF₃ alkynes under the influence of an Ru catalyst has been reported, see:

42b Kawatsura M, Yamamoto M, Namioka J, Kajita K, Hirakawa T, Itoh T. Org. Lett. 2011; 13: 1001

Trifluoromethylated Internal Alkynes: Versatile Building Blocks for the ­Preparation of Various Fluorine-Containing Molecules

Trifluoromethylated Internal Alkynes: Versatile Building Blocks for the Preparation of Various Fluorine-Containing Molecules