The Nef Reaction of Isocyanides

Fabio La Spisa; Gian Cesare Tron; Laurent El Kaïm

doi:10.1055/s-0033-1338596

Synthesis, Table of Contents

Synthesis 2014; 46(07): 829-841
DOI: 10.1055/s-0033-1338596

review

The Nef Reaction of Isocyanides

Fabio La Spisa

^aDipartimento di Scienze del Farmaco, Università degli Studi del Piemonte Orientale ‘A. Avogadro’, Largo Donegani 2, 28100 Novara, Italy Email: tron@pharm.unipmn.it

,

Gian Cesare Tron*

^aDipartimento di Scienze del Farmaco, Università degli Studi del Piemonte Orientale ‘A. Avogadro’, Largo Donegani 2, 28100 Novara, Italy Email: tron@pharm.unipmn.it

,

Laurent El Kaïm*

^bUMR 7652 (Ecole Polytechnique/ENSTA/CNRS), Laboratoire Chimie et Procédés, ENSTA-Paristech, 828 Bd des maréchaux, 91120 Palaiseau, France Email: laurent.elkaim@ensta-paristech.fr

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Abstract

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Abstract

The interaction of isocyanides with acyl chlorides was first reported by Nef in 1892. The resulting α-keto imidoyl chlorides may be hydrolyzed to form α-keto amides. Relatively few data are available on this reaction and the chemistry of α-keto imidoyl chlorides has been largely underestimated until some recent uses in intra- and intermolecular couplings with a variety of nucleophiles. The present review brings a comprehensive presentation of the Nef reaction of isocyanides focusing on mechanism and regioselectivity issues.

1 Isocyanide Chemistry

2 Isocyanide Interaction with Acyl Chlorides and Analogues

2.1 General Considerations

2.2 Methods of Preparation of α-Keto Imidoyl Chlorides

2.3 Nef Reaction Mechanism

3 Reactivity of α-Keto Imidoyl Chlorides

3.1 General Behavior of α-Keto Imidoyl Chlorides

3.2 Intramolecular Trappings

3.3 Intermolecular Trappings and Three-Component Reactions

4 Extensions of the Nef Reaction

5 Conclusion

Key words

isocyanides - Nef reaction - acyl chlorides - imidoyl chlorides - ketenes

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References

References

For reviews concerning Ugi couplings, see:

1a Zhu J. Eur. J. Org. Chem. 2003; 1133
1b Ugi I, Werner B, Dömling A. Molecules 2003; 8: 53
1c Hulme C, Gore V. Curr. Med. Chem. 2003; 10: 51
1d Bienaymé H, Hulme C, Oddon G, Schmitt P. Chem. Eur. J. 2000; 6: 3321
1e Dömling A, Ugi I. Angew. Chem. Int. Ed. 2000; 39: 3168
1f Dömling A. Chem. Rev. 2006; 106: 17
1g El Kaim L, Grimaud L. Tetrahedron 2009; 65: 2153

2a Malatesta L, Bonati F. Isocyanide complexes of metals. J. Wiley; London: 1969: 131-143
2b Vogler A. Coordinated isocyanide. In Isonitrile Chemistry. Ugi I. Academic Press; London: 1971. Chapt. 10, 217-233
2c Kuznetsov ML. Russ. Chem. Rev. 2002; 71: 265

3 Nanni D. Isonitriles: Useful Traps in Radical Chemistry, In Radicals in Organic Synthesis . Vol. 2. Renaud P, Sibi MP. Wiley–VCH; Weinheim: 2001: 44-61
4 Passerini M. Gazz. Chim. Ital. 1921; 51: 126
5 Lieke W. Ann. Chem. Pharm. 1859; 112: 316
6 Nef JU. Justus Liebigs Ann. Chem. 1892; 270: 267
7 Obrecht R, Herrmann R, Ugi I. Synthesis 1985; 400
8 Nef JU. Justus Liebigs Ann. Chem. 1894; 280: 263
9 Nef JU. Justus Liebigs Ann. Chem. 1900; 310: 316
10 Nef worked mainly alone, and except for three research articles, he never published with a co-worker. His nature was temperamental and impulsive, and he demanded of his students order and cleanliness in the lab. For a biography, see: Wolfrom ML. Biogr. Memoirs Natl. Acad. Sci. 1960; 34: 204
11 Ugi I, Fetzer U. Chem. Ber. 1961; 94: 1116
12 Ugi I, Beck F, Fetzer U. Chem. Ber. 1962; 95: 126

13a Barret AG. M, Barton DH. R, Falck JR, Papaioannou D, Widdowson DA. J. Chem. Soc., Perkin Trans. 1 1979; 652
13b Adlington RM, Barrett AG. M. Chem. Commun. 1981; 65
13c Chen JJ, Deshpande SV. Tetrahedron Lett. 2003; 44: 8873

14 Westling M, Smith R, Livinghouse T. J. Org. Chem. 1986; 51: 1159

15a Tian W.-S, Livinghouse T. Chem. Commun. 1989; 819
15b Capuano L, Hell W, Wamprecht C. Liebigs Ann. Chem. 1986; 132

16a El Kaïm L. Tetrahedron Lett. 1994; 35: 6669
16b El Kaïm L, Pinot-Périgord E. Tetrahedron 1998; 54: 3799
16c Huang W.-S, Zhang Y.-X, Yuan C. J. Chem. Soc., Perkin Trans. 1 1996; 1893

17 Suginome M, Ito Y. Adv. Polym. Sci. 2004; 171: 77
18 Gian Cesare Tron, personal communication.

19a Aller E, Molina P, Lorenzo A. Synlett 2000; 526
19b Bio MM, Javadi G, Song ZJ. Synthesis 2005; 19
19c Cui L, Liu Q, Yu J, Ni C, Yu H. Tetrahedron Lett. 2011; 52: 5530

20 Authors of this review have noted a great instability of the α-keto imidoyl chlorides derived from N-isocyanotriphenyl-iminophosphorane, which, in the presence of adventitious water, reacts to give the keto hydrazidoyl chlorides.
21 Coffinier D, El Kaïm L, Grimaud L. Org. Lett. 2009; 11: 1825
22 Yavari I, Pashazadeh R, Hosseinpour R, Ghanbari E. Tetrahedron Lett. 2013; 54: 2785
23 Westling M, Livinghouse T. Tetrahedron 1985; 26: 5389
24 Chéron N, El Kaïm L, Grimaud L, Fleurat-Lessard P. J. Phys. Chem. 2011; 115: 10106
25 Chéron N, Jacquemin D, Fleurat-Lessard P. Phys. Chem. Chem. Phys. 2012; 14: 7170
26 Lu L, Hu H, Hou H, Wang B. Comp. Theor. Chem. 2013; 1015, 64
27 Rügheimer L, Schramm CG. Ber. Dtsch. Chem. Ges. 1888; 21: 299
28 Bonne R. Imidoyl halides. In The chemistry of the carbon-nitrogen double bond . Patai S. John Wiley & Sons; New York: 1970: 597-662
29 Hughes DJ, Livinghouse T. J. Chem. Soc., Perkin Trans. 1 1995; 2373
30 Luedtke G, Livinghouse T. J. Chem. Soc., Perkin Trans. 1 1995; 2369
31 Westling M, Smith R, Livinghouse T. J. Am. Chem. Soc. 1987; 109: 590
32 Lee CH, Westling M, Livinghouse T, Williams AC. J. Am. Chem. Soc. 1992; 114: 4089
33 VanWagenen BC, Cardellina JH. Tetrahedron Lett. 1989; 30: 3605
34 Livinghouse T. Tetrahedron 1999; 55: 9947
35 Huang WS, Zhang YX, Yuan CY. Synth. Commun. 1996; 26: 6: 1149

36a Dos Santos A, El Kaïm L, Grimaud L, Ronsseray C. Chem. Commun. 2009; 3907
36b El Kaïm L, Grimaud L, Schiltz A. Tetrahedron Lett. 2009; 50: 5235

37 Lau HH, Schöllkopf U. Liebigs Ann. Chem. 1982; 2093
38 After deprotonation, the α-effect raises the energy of the nitrogen lone pair which is responsible for the dechlorination. The mechanism is reminiscent of those for the preparation of nitrile N-oxides via hydroximoyl chlorides.

39a Walter W, Bode K.-D. Justus Liebigs Ann. Chem. 1966; 698: 131
39b Walter W, Bode K.-D. Angew. Chem. Int. Ed. 1962; 1: 510

40 El Kaïm L, Grimaud L, Wagschal S. Synlett 2009; 1315
41 Coffinier D, El Kaïm L, Grimaud L. Synlett 2008; 1133
42 Coffinier D, El Kaïm L, Grimaud L. Synlett 2010; 2474
43 Coffinier D, El Kaïm L, Grimaud L, Ruijter E, Orru RV. A. Tetrahedron Lett. 2011; 52: 3023
44 Yavari I, Pashazadeh R, Hosseinpour R, Ghanbari E, Skoulika S. Tetrahedron 2013; 69: 2462
45 Yavari I, Hosseinpour R, Pashazadeh R. Synlett 2012; 23: 1662
46 Yavari I, Pashazadeh R, Hosseinpour R. Helv. Chim. Acta 2012; 95: 169
47 Krivinka P, Honzl J. Coll. Czech. Chem. Commun. 1972; 37: 4035
48 Ripka AS, Diaz DD, Sharpless KB, Finn MG. Org. Lett. 2003; 5: 1531
49 Ugi I, Rosendahl K. Chem. Ber. 1961; 94: 2233
50 El Gomati T, Firl J, Ugi I. Chem. Ber. 1977; 110: 2012
51 X-ray diffraction studies confirmed the latter structure, see: Robertson J, Bell SJ, Krivokapic A. Org. Biomol. Chem. 2005; 3: 4246
52 Capuano L, Tammer T. Chem. Ber. 1981; 114: 456

53a Capuano L, Dahm B, Port V, Schnur R, Schramm V. Chem. Ber. 1988; 121: 271
53b A similar reaction using silyl vinyl ketenes and isocyanides to give substituted cyclopentenones has also been reported, see: Li Z, Moser WH, Deng R, Sun L. J. Org. Chem. 2007; 72: 10254

54 Mossetti R, Pirali T, Tron GC, Zhu J. Org. Lett. 2010; 12: 820

55a Mossetti R, Caprioglio D, Colombano G, Tron GC, Pirali T. Org. Biomol. Chem. 2011; 9: 1627
55b Basch CH, Brinck JA, Ramos JE, Habay SA, Yap GP. A. J. Org. Chem. 2012; 77: 10416

56 Wu J, Chen W, Hu M, Zou H, Yu Y. Org. Lett. 2010; 12: 616
57 Basso A, Banfi L, Garbarino S, Riva R. Angew. Chem. Int. Ed. 2013; 52: 2096
58 For a similar reaction between isocyanides and two equivalents of arylacetic acids, see: Basso A, Banfi L, Galatini A, Guanti G, Rastrelli F, Riva R. Org. Lett. 2009; 11: 4068