Subscribe to RSS
DOI: 10.1055/s-0033-1340867
Trifluoromethylated Internal Alkynes: Versatile Building Blocks for the Preparation of Various Fluorine-Containing Molecules
Publication History
Received: 05 January 2014
Accepted after revision: 04 February 2014
Publication Date:
11 April 2014 (online)
![](https://www.thieme-connect.de/media/synlett/201410/lookinside/thumbnails/10.1055-s-0033-1340867-1.jpg)
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
-
References
- 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
- 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
- 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
- 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
- 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
- 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
- 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
- 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
- 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
- 41b Garcia JJ, Sierra C, Torrens H. Tetrahedron Lett. 1996; 37: 6097
For reviews, see:
For reports on the preparation of CF3 alkynes published prior to 2000, see:
For reports on the preparation of CF3 alkynes published since 2000, see:
For other synthetic applications of CF3 alkynes, see:
It has been reported that various CF3 propargylamines can be prepared through the reaction of a CF3 acetylide with N-sulfinylimines, see:
For palladium-catalyzed carbostannylation reactions, see:
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:
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:
The addition reaction of phenol or thiophenol toward CF3 alkynes has been reported, see:
For pioneering work, see: