Direct Synthesis of Bis(alkylamino)maleonitriles from Alcohols and TMSCN with Bi(OTf)₃

Abstract

A direct method for preparing bis(alkylamino)maleonitriles from alcohols was developed. Treatment of tertiary alcohols 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-to-high yields. Tertiary alcohols with various functional groups such as halo, ether, ester, and imide­ functional groups were tolerated under these conditions. This is the first report of a synthetic method for the preparation of bis(alkylamino)maleonitriles in a single step from tertiary alcohols.

Key words

alcohols - Lewis acid - bismuth - maleonitrile - cyanides

• 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 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
• 1e Bittermann A, Härter P, Herdtweck E, Hoffmann SD, Herrmann WA. J. Organomet. Chem. 2008; 693: 2079
• 1f Goslinski T, Dutkiewicz Z, Kryjewski M, Tykarska E, Sobotta L, Szczolko W, Gdaniec M, Mielcarek J. Monatsh. Chem. 2011; 142: 599
• 1g Schwarze T, Kelling A, Müller H, Trautmann M, Klamroth T, Baumann O, Strauch P, Holdt H.-J. Chem. Eur. J. 2012; 18: 10506
• 1h 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
• 4a Kitano Y, Chiba K, Tada M. Tetrahedron Lett. 1998; 39: 1911
• 4b Kitano Y, Chiba K, Tada M. Synlett 1999; 288
• 4c Kitano Y, Chiba K, Tada M. Synthesis 2001; 437
• 4d Kitano Y, Manoda T, Miura T, Chiba K, Tada M. Synthesis 2006; 405
• 4e Okada I, Kitano Y. Synthesis 2011; 3997
• 5a Bothwell JM, Krabbe SW, Mohan RS. Chem. Soc. Rev. 2011; 40: 4649
• 5b Suresh Sandhu JS. Rasayan J. Chem. 2011; 4: 73 ; http://rasayanjournal.co.in/index.html
• 5c Rueping M, Nachtsheim BJ. Top. Curr. Chem. 2012; 311: 115
• 6a Wu F, Mandadapu V, Day AI. Tetrahedron 2013; 69: 9957
• 6b Hayashi R, Park J, Cook GR. Heterocycles 2014; 88: 1477
• 6c Chouguiat L, Boulcina R, Debache A. J. Chem. Pharm. Res. 2014; 6: 79
• 6d Raju BC, Prasad KV, Saidachary G, Sridhar B. Org. Lett. 2014; 16: 420
• 6e Abd ME, Aleen E, El-Remaily A. Chin. J. Catal. 2015; 36: 1124
• 6f Lyu L, Jin MY, He Q, Xie H, Bian Z, Wang J. Org. Biomol. Chem. 2016; 14: 8088
• 7a Guchhait SK, Priyadarshania G, Gulghanea NM. RSC Adv. 2016; 6: 56056
• 7b Chen T, Cai C. Catal. Commun. 2016; 74: 119
• 7c Maleki A, Akhlaghi E, Paydar R. Appl. Organomet. Chem. 2016; 30: 382
• 8 Chen HG, Goel OP, Kesten S, Knobelsdolf J. Tetrahedron Lett. 1996; 37: 8129
• 9 Pronin SV, Reiher CA, Shenvi RA. Nature (London) 2013; 501: 195
• 10a Shaabani A, Maleki A, Mofakham H, Moghimi-Rad J. J. Org. Chem. 2008; 73: 3925
• 10b Maleki A. Tetrahedron 2012; 68: 7827
• 10c Maleki A. Tetrahedron Lett. 2013; 54: 2055