Subscribe to RSS
Please copy the URL and add it into your RSS Feed Reader.
https://www.thieme-connect.de/rss/thieme/en/10.1055-s-00000084.xml
Synthesis 2012; 44(15): 2436-2440
DOI: 10.1055/s-0032-1316553
DOI: 10.1055/s-0032-1316553
paper
Nucleophilic Pentafluorophenylation of Nitroalkenes
Further Information
Publication History
Received: 17 April 2012
Accepted after revision: 22 May 2012
Publication Date:
27 June 2012 (online)

Abstract
The interaction of pentafluorophenylmagnesium bromide with conjugate nitroalkenes is described. The optimized conditions involve performing the reaction either in diethyl ether in the presence of chlorotrimethylsilane or in a tetrahydrofuran–diethyl ether solvent mixture. The addition products can be transformed into 4,5,6,7-tetrafluoroindolines by means of a reduction and cyclization sequence.
-
References
- 1a Boudakian MM In Kirk-Othmer Encyclopedia of Chemical Technology . John Wiley & Sons, Inc; Weinheim: 2000
- 1b Kirsch P. Modern Fluoroorganic Chemistry . Wiley-VCH; Weinheim: 2004
- 2a Kim C.-Y, Chang JS, Doyon JB, Baird TT, Fierke CA, Jain A, Christianson DW. J. Am. Chem. Soc. 2000; 122: 12125
- 2b Kim C.-Y, Chandra PP, Jain A, Christianson DW. J. Am. Chem. Soc. 2001; 123: 9620
- 3a Gdaniec M, Jankowski W, Milewska MJ, Polonski T. Angew. Chem. Int. Ed. 2003; 42: 3903
- 3b Korenaga T, Kawauchi Y, Kosaki T, Ema T, Sakai T. Bull. Chem. Soc. Jpn. 2005; 78: 2175
- 3c Zahn A, Brotschi C, Leumann CJ. Chem.–Eur. J. 2005; 11: 2125
- 3d Lakshminarayanan PS, Ravikumar I, Suresh E, Ghosh P. Inorg. Chem. 2007; 46: 4769
- 4a Francesch L, Borros S, Knoll W, Förch R. Langmuir 2007; 23: 3927
- 4b Blanchard MD, Hughes RP, Concolino TE, Rheingold AL. Chem. Mater. 2000; 12: 1604
- 5a Kvicala J, Benes M, Paleta O, Kral V. J. Fluorine Chem. 2010; 131: 1327
- 5b Pazitny A, Solcan T, Vegh D. J. Fluorine Chem. 2009; 130: 267
- 6a Korenaga T, Kosaki T, Fukumura R, Ema T, Sakai T. Org. Lett. 2005; 7: 4915
- 6b Zhong W, Liu Z, Yu C, Su W. Synlett 2008; 2888
- 6c Kovtonyuk VN, Kobrina LS, Haufe G. Russ. Chem. Bull. 2008; 57: 1686
- 6d Chen QY, Li ZT. J. Org. Chem. 1993; 58: 2599
- 7a Prakash GK. S, Yudin AK. Chem. Rev. 1997; 97: 757
- 7b Brogan S, Carter NB, Lam HW. Synlett 2010; 615
- 7c Coe PL, Stephens R, Tatlow JC. J. Chem. Soc. 1962; 3227
- 7d Dilman AD, Belyakov PA, Korlyukov AA, Struchkova MI, Tartakovsky VA. Org. Lett. 2005; 7: 2913
- 7e Dilman AD, Levin VV, Belyakov PA, Struchkova MI, Tartakovsky VA. Synthesis 2006; 447
- 7f Levin VV, Dilman AD, Belyakov PA, Korlyukov AA, Struchkova MI, Antipin MY, Tartakovsky VA. Synthesis 2006; 489
- 8a Dilman AD, Levin VV, Belyakov PA, Struchkova MI, Tartakovsky VA. Tetrahedron Lett. 2008; 49: 4352
- 8b Zemtsov AA, Levin VV, Dilman AD, Struchkova MI, Belyakov PA, Tartakovsky VA. Tetrahedron Lett. 2009; 50: 2998
- 8c Zemtsov AA, Levin VV, Dilman AD, Struchkova MI, Belyakov PA, Tartakovsky VA, Hu J. Eur. J. Org. Chem. 2010; 6779
- 8d Zemtsov AA, Levin VV, Dilman AD, Struchkova MI, Tartakovsky VA. J. Fluorine Chem. 2011; 132: 378
- 9 An example of conjugate addition of C6F5MgBr to cyclic unsaturated ester generated in situ was reported, see: Claremon DA, McClure DE, Springer JP, Baldwin JJ. J. Org. Chem. 1984; 49: 3871
- 10a Furukawa T, Nishimine T, Tokunaga E, Hasegawa K, Shiro M, Shibata N. Org. Lett. 2011; 13: 3972
- 10b Li Y, Liang F, Li Q, Xu Y.-c, Wang Q.-R, Jiang L. Org. Lett. 2011; 13: 6082
- 11 Kawai H, Tachi K, Tokunaga E, Shiro M, Shibata N. Angew. Chem. Int. Ed. 2011; 50: 7803
- 12 Dilman AD, Arkhipov DE, Korlyukov AA, Ananikov VP, Danilenko VM, Tartakovsky VA. J. Organomet. Chem. 2005; 690: 3680
- 13 Silylating reagents are typical additives in cuprate additions to unsaturated carbonyl compounds, see: Dilman AD, Ioffe SL. Chem. Rev. 2003; 103: 733
- 14a Filler R, Chen W, Woods SM. J. Fluorine Chem. 1995; 73: 95
- 14b Filler R, Woods SM, White WL. Can. J. Chem. 1989; 67: 1837
- 15 Worrall DE. Org. Synth. 1929; 9: 66
- 16 Romashov LV, Khomutova YA, Danilenko VM, Ioffe SL, Lesiv AV. Synthesis 2010; 407
- 17 Heinzelman RV. Org. Synth. 1955; 35: 74
- 18 Melton J, McMurry JE. J. Org. Chem. 1975; 40: 2138
- 19 Mikesell P, Schwaebe M, DiMare M, Little RD. Acta Chem. Scand. 1999; 53: 792
- 20 Node M, Nagasawa H, Naniwa Y, Fuji K. Synthesis 1987; 729
- 21 Gao S, Tu YQ, Hu X, Wang S, Hua R, Jiang Y, Zhao Y, Fan X, Zhang S. Org. Lett. 2006; 8: 2373
- 22 Gate EN, Threadgill MD, Stevens MF. G, Chubb D, Vickers LM, Langdon SP, Hickman JA, Gescher A. J. Med. Chem. 1986; 29: 1046
Acylated Baylis–Hillman adducts also were subjected to nucleophilic pentafluorophenylation and trifluoromethylation reactions, which proceed through attack of the carbanion at the C=C bond, see ref. 8c and