Catalytic Reductive Etherification of Ketones with Alcohols at Ambient Hydrogen Pressure: A Practical, Waste-Minimized Synthesis of Dialkyl Ethers

Abstract

A heterogeneous platinum catalyst was found to efficiently mediate the reductive etherification of ketones at ambient hydrogen pressure. In this environmentally benign transformation, water is released as the only by-product, and this is trapped with molecular sieves. The preparative utility of the new reaction protocol is demonstrated by the synthesis of ten unsymmetrical ethers from the corresponding ketones and primary or secondary alcohols.

Key words

ethers - reductive etherification - platinum - catalysis - hydrogenation

References

• 1 Williamson AW. Justus Liebigs Ann. Chem.  1851,  77:  37 
• 2a March J. In Advanced Organic Chemistry   3rd ed.:  Wiley; New York: 1992.  p.386-387  
• 2b Sweeney JB. Gen. Synth. Methods  1992,  14:  138 
• 2c Meerwein H. In Houben-Weyl   4th ed., Vol. VI/3:  Müller E. Thieme; Stuttgart: 1965.  p.24 
• 2d Freedman HH. Dubois RA. Tetrahedron Lett.  1975,  3251 
• For reviews, see for example:
• 3a Gomez S. Peters JA. Maschmeyer T. Adv. Synth. Catal.  2002,  344:  1037 
• 3b Rylander PN. In Catalytic Hydrogenation over Platinum Metals   Academic Press; New York: 1967.  p.291 
• 4a Verzele M. Acke M. Anteunis M. J. Chem. Soc.  1963,  5598 
• 4b Beckwith ALJ. Gilpin ML. J. Chem. Soc., Perkin Trans. 1  1977,  19 
• 5 Verhoef MJ. Creyghton EJ. Peters JA. van Bekkum H. Chem. Commun.  1997,  1989 
• 6 Bethmont V. Fache F. Lemaire M. Tetrahedron Lett.  1995,  4235 
• 7 Fujii Y. Furugaki H. Yano S. Kita K. Chem. Lett.  2000,  926 
• 8a Doyle MP. DeBruyn DJ. Kooista DA. J. Am. Chem. Soc.  1972,  3659 
• 8b Nicolaou KC. Hwang C.-K. Nugiel DA. J. Am. Chem. Soc.  1989,  111:  4136 
• 8c Wada M. Nagayama S. Mitzutani K. Hiroi R. Miyoshi N. Chem. Lett.  2002,  248 
• 8d Suzuki T. Ohashi K. Oriyama T. Synthesis  1999,  1561 
• 9a Kato J. Iwasawa N. Mukaiyama T. Chem. Lett.  1985,  743 
• 9b Sassaman MB. Kotian KD. Prakash GKS. Olah GA. J. Org. Chem.  1987,  4314 
• 9c Hatakeyama S. Mori H. Kitano K. Yamada H. Nishizawa M. Tetrahedron Lett.  1994,  4367 
• 9d Komatsu N. Ishida J. Suzuki H. Tetrahedron Lett.  1997,  7219 
• 9e Miura K. Ootsuka K. Suda S. Nishikori H. Hosomi A. Synlett  2002,  313