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DOI: 10.1055/s-0037-1610865
A New Method for the Preparation of Bis(alkylamino)maleonitriles from Aliphatic Isocyanides with TMSCN and Bi(OTf)3
This work was partially supported by JSPS KAKENHI Grant Number JP16K07867.Publication History
Received: 17 January 2019
Accepted after revision: 04 February 2019
Publication Date:
11 March 2019 (online)
Abstract
Bis(alkylamino)maleonitriles are starting materials for the synthesis of a number of important intermediates, including porphyrazines that serve as dyes, pigments, and models of biologically active substances; hence, the development of improved methods for their preparation is important. Herein, we report a facile new method for the preparation of bis(alkylamino)maleonitriles from isocyanides. Treatment of tert-alkyl isocyanides with trimethylsilyl cyanide (TMSCN) and trimethylsilyl triflate (TMSOTf) in the presence of bismuth(III) triflate [Bi(OTf)3] afforded the corresponding bis(alkylamino)maleonitriles in moderate yields. tert-Alkyl isocyanides bearing a variety of functional groups, including halide, ether, ester, imide, amide, and carbamate, are tolerated under the developed reaction conditions. To the best of our knowledge, this is the first report of a synthetic method for the preparation of bis(alkylamino)maleonitriles in a single step from tertiary alkyl isocyanides.
Supporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/s-0037-1610865.
- Supporting Information
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References
- 1a Kopranenkov VN, Goncharova LS, Luk’yanets EA. Zh. Org. Khim. 1979; 15: 1076
- 1b Beall LS, Mani NS, White AJ. P, Williams DJ, Barrett AG. M, Hoffman BM. J. Org. Chem. 1998; 63: 5806
- 1c Baum SM, Trabanco AA, Montalban AG, Micallef AS, Zhong C, Meunier HG, Suhling K, Phillips D, White AJ. P, Williams DJ, Barrett AG. M, Hoffman BM. J. Org. Chem. 2003; 68: 1665
- 1d Al-Azmi A, Elassar AA.-Z, Booth LB. Tetrahedron 2003; 59: 2749
- 1e Fuchter MJ, Beall LS, Baum SM, Montalban AG, Sakellariou EG, Mani NS, Miller T, Vesper BJ, White AJ. P, Williams DJ, Barrett AG. M, Hoffman BM. Tetrahedron 2005; 61: 6115
- 1f Bittermann A, Härter P, Herdtweck E, Hoffmann SD, Herrmann WA. J. Organomet. Chem. 2008; 693: 2079
- 1g Goslinski T, Dutkiewicz Z, Kryjewski M, Tykarska E, Sobotta L, Szczolko W, Gdaniec M, Mielcarek J. Monatsh. Chem. 2011; 142: 599
- 1h Schwarze T, Kelling A, Müller H, Trautmann M, Klamroth T, Baumann O, Strauch P, Holdt H.-J. Chem. Eur. J. 2012; 18: 10506
- 1i Baier H, Metzner P, Körzdörfer T, Kelling A, Holdt H.-J. Eur. J. Inorg. Chem. 2014; 2952
- 2a Begland RW, Hartter DR, Jones FN, Sam DJ, Sheppard WA, Webster OW, Weigert FJ. J. Org. Chem. 1974; 39: 2341
- 2b Prabahar KJ, Shanmugasundaram P, Ramakrishnan VT. Indian J. Chem., Sect. B: Org. Chem. Incl. Med. Chem. 1992; 31: 563
- 3a Honzl J, Křivinka P. Tetrahedron Lett. 1970; 11: 2357
- 3b Vries LD. J. Org. Chem. 1971; 36: 3442
- 3c Boyer JH, Kooi J. J. Am. Chem. Soc. 1976; 98: 1099
- 4 Okada I, Fukuda T, Kuroda Y, Noguchi K, Chiba K, Kitano Y. Synthesis 2017; 49: 1301
- 5a Kitano Y, Chiba K, Tada M. Tetrahedron Lett. 1998; 39: 1911
- 5b Kitano Y, Chiba K, Tada M. Synlett 1999; 288
- 5c Kitano Y, Chiba K, Tada M. Synthesis 2001; 437
- 5d Kitano Y, Manoda T, Miura T, Chiba K, Tada M. Synthesis 2006; 405
- 5e Kobayashi G, Saito T, Kitano Y. Synthesis 2011; 3225
- 5f Okada I, Kitano Y. Synthesis 2011; 3997
- 6 Chen HG, Goel OP, Kesten S, Knobelsdolf J. Tetrahedron Lett. 1996; 37: 8129
- 7a Shaabani A, Maleki A, Mofakham H, Moghimi-Rad J. J. Org. Chem. 2008; 73: 3925
- 7b Maleki A. Tetrahedron 2012; 68: 7827
- 7c Maleki A. Tetrahedron Lett. 2013; 54: 2055
- 8a Bothwell JM, Krabbe SW, Mohan RS. Chem. Soc. Rev. 2011; 40: 4649
- 8b Suresh, Sandhu JS. Rasayan J. Chem. 2011; 4: 73
- 8c Rueping M, Nachtsheim BJ. Top. Curr. Chem. 2012; 311: 115
- 9 Kitano Y, Nogata Y, Matsumura K, Yoshimura E, Chiba K, Tada M, Sakaguchi I. Tetrahedron 2005; 61: 9969
- 10 Okada I, Chiba K, Kitano Y. Synthesis 2013; 45: 1069