Mild and Efficient Silylcyanation of Ketones Catalyzed by N-Methylmorpholine N-Oxide

Abstract

An efficient method for achiral addition of TMSCN to ketones by employing N-methylmorpholine N-oxide (NMO) alone as the catalyst is described. A variety of aromatic, aliphatic, cyclic and heterocyclic ketones are converted into their corresponding trimethylsilyl ethers in excellent yields (>90%).

Key words

silylcyanation - NMO - TMSCN - ketone - cyanohydrins

References

• 2 Griengel H. Hickel A. Johnson DV. Kratky C. Schmidt M. Schwab H. Chem. Commun.  1997,  1933 ; and references cited therein
• 3a Gregory RJH. Chem. Rev.  1999,  99:  3649 
• 3b Shan GM. Hammer RP. Ottea JA. J. Agric. Food Chem.  1997,  45:  4466 
• 3c Galin FZ. Rakhimov RH. Tolstikov GA. Russ. Chem. Bull.  1998,  47:  530 
• 4a North M. Synlett  1993,  807 
• 4b Deng H. Ister MP. Snapper ML. Hoveyda AH. Angew. Chem., Int. Ed.  2002,  41:  1009 
• 4c Tanaka K. Mori A. Inoue S. J. Org. Chem.  1990,  55:  181 
• 4d Hayashi M. Miyamoto Y. Inoue T. Oguni N. J. Org.Chem.  1993,  58:  1515 
• 4e Kobayashi S. Tsuchiya Y. Mukaiyama T. Chem. Lett.  1991,  537 
• 4f Hanashima Y. Sawada D. Nogami H. Kanai M. Shibasaki M. Tetrahedron  2001,  57:  805 
• 4g Tian SK. Hong R. Deng L. J. Am. Chem. Soc.  2003,  125:  9900 
• 5a Tararov VI. Hibbs DE. Hursthouse MB. Ikonnikov NS. Abdul Malik KM. North M. Orizu C. Belokon Y. Chem. Commun.  1998,  387 
• 5b Belokon Y. Green B. Ikonnikov NS. North M. Tararov VI. Tetrahedron Lett.  1999,  40:  8147 
• 5c Belokon Y. Green B. Ikonnikov NS. North M. Parsons T. Tararov VI. Tetrahedron  2001,  57:  771 
• 6a Hanashima Y. Kanai M. Shibasaki M. J. Am. Chem. Soc.  2000,  122:  7412 
• 6b Hanashima Y. Kanai M. Shibasaki M. Tetrahedron Lett.  2001,  42:  691 
• 6c Yabu K. Masumoto S. Yamasaki S. Hamashima Y. Kanai M. Du W. Curran DP. Shibasaki M. J. Am. Chem. Soc.  2001,  123:  9908 
• 7 Bolm C. Muller P. Tetrahedron Lett.  1995,  36:  1625 
• 8 Rowlands GJ. Synlett  2003,  236 
• 9 Chen F. Feng X. Qin B. Zhang G. Jiang Y. Org. Lett.  2003,  5:  949 
• 10 Belokon Y. North M. Parsons T. Org. Lett.  2000,  2:  1617 
• 11 Aspinall HC. Greeves N. Smith PM. Tetrahedron Lett.  1999,  40:  1763 
• 12 Bandini M. Cozzi PG. Melchiorre P. Ronchi AV. Tetrahedron Lett.  2001,  42:  3041 
• 13a Whitesell JK. Podaca RA. Tetrahedron Lett.  1996,  37:  2525 
• 13b Saravanan P. Vijaya Anand R. Singh VK. Tetrahedron Lett.  1998,  39:  3823 
• 14 Curini M. Epifano F. Marcotullio MC. Rosati O. Rossi M. Synlett  2002,  315 
• 15 Chen F. Feng X. Qin B. Zhang G. Jiang Y. Synlett  2003,  558 
• 16a Shen Y. Feng X. Li Y. Zhang G. Jiang Y. Tetrahedron  2003,  59:  5667 
• 16b Shen Y. Feng X. Li Y. Zhang G. Jiang Y. Synlett  2002,  793 
• 17 Nakajima M. Saito M. Shiro M. Hashimoto SI. J. Am. Chem. Soc.  1998,  120:  6419 
• 18 Derdau V. Laschat S. Hupe E. Konig WA. Dix I. Jones PG. Eur. J. Inorg. Chem.  1999,  1001 
• 19 O’Neil IA. Turner CD. Kalindjian SB. Synlett  1997,  777 

1

Dr. G. Rajagopal is a Brain Pool Scientist from Department of Chemistry, Crescent Engineering College, Chennai 600 048, India, and is assisted by a grant from the Korean Federation of Science and Technology Societies and Korea Science and Engineering Foundation.