Synthesis of α,β-Epoxy Ketones from Alkyl- and Arylsubstituted Cyclopropanols

Abstract

A number of aliphatic and arylaliphatic α,β-epoxy ketones were prepared in good yields in a one-pot procedure by a manganese-catalyzed ring cleavage of 1-substituted and 1,2-disubstituted cyclopropanols with oxygen followed by dehydration of the resulting cyclic peroxides with alkali.

Key words

epoxides - ketones - cyclopropanes - oxidations - transition metals

References and Notes

• 1 Morisson V. Barnier J.-P. Blanco L. Tetrahedron Lett.  1999,  40:  4045 
• 2 Barnier J.-P. Morisson V. Blanco L. Synth. Commun.  2001,  349 
• For noncatalytic oxidation of cyclopropanols and related compounds to cyclic peroxides, see:
• 3a Gibson DH. DePuy CH. Tetrahedron Lett.  1969,  2203 
• 3b Ceccherelli P. Curini M. Coccia R. Diamantini M. J. Chem. Soc., Perkin Trans. 1  1984,  1693 
• 3c Scheller ME. Mathies P. Petter W. Frei B. Helv. Chim. Acta  1984,  67:  1748 
• 4 For CuCl₂-catalyzed oxygenation of 1-pyrrolidinobicyclo-[n.1.0]alkanes providing in low yield 2,3-epoxycyclo-alkanones in the absence of a base, see: Itoh T. Kaneda K. Teranishi S. Tetrahedron Lett.  1975,  2801 
• 5a Payne GB. J. Org. Chem.  1958,  23:  310 
• 5b Paquette LA. Carr RVC. Bellamy F. J. Am. Chem. Soc.  1978,  100:  6764 
• For recent applications of aliphatic and arylaliphatic α,β-epoxy ketones in the synthesis of natural compounds, see:
• 6a Takayama H. Kurihara M. Kitajima M. Said IM. Aimi N. J. Org. Chem.  1999,  64:  1772 
• 6b Hirose T. Sunazuka T. Zhi-Ming T. Handa M. Uchida R. Shiomi K. Harigaya Y. Omura S. Heterocycles  2000,  53:  777 
• 7 For a review, see: Kulinkovich OG. de Meijere A. Chem. Rev.  2000,  100:  2789 
• 9 Reichel L. Neubauer A. Liebigs Ann. Chem.  1975,  1538 
• 10 We found that the reaction of cyclopropanol 1e with O₂ in the presence of tri-n-butylvanadate(V) resulted in the formation of hemiacetal 2e and known β-hydroxy ketone 8e (Scheme 2). After treatment of the reaction mixture produced from the above oxidation of 1e with LiCuCl₂ solution in THF (0.25 M, 50 mol%), compound 8e was obtained in 46 % overall yield. For physical and spectral data of 8e, see: Gaudemar-Bardone F. Gaudemar M. J. Organomet. Chem.  1976,  104:  281 
• 11 Compare: Kirihara M. Ichinose M. Takizawa S. Momose T. Chem. Commun.  1998,  1691 
• 12 Kulinkovich OG. Vasilevsky DA. Savchenko AI. Sviridov SV. Zh. Org. Khim.  1991,  27:  1428 
• 13 Kulinkovich OG. Savchenko AI. Sviridov SV. Vasilevsky DA. Mendeleev Commun.  1993,  230 
• 14a Tishchenko IG. Bubel ON. Zyatkov IP. Zh. Obshch. Khim.  1963,  33:  2613 
• 14c Sato K. Aoki M. Ogawa M. Hashimoto T. Panyella D. Noyori R. Bull. Chem. Soc. Jpn.  1997,  70:  905 
• 15 House OH. Reif DJ. J. Am. Chem. Soc.  1955,  77:  6525 
• 16a Temnicova TI. Martynov VF. Zh. Obshch. Khim.  1945,  15:  499 
• 17a Tishchenko IG. Skupskaya RV. Vestsi Akad. Navuk BSSR, Ser. Khim. Navuk  1965,  72 
• 18a Tishchenko IG. Naumova LV. Remizov PP. Khim. Geterotsikl. Soedin.  1965,  5:  643 
• 19 Tishchenko IG. Sytin VN. Revinskii IF. Zh. Org. Khim.  1977,  13:  1154 

8

The rate of oxidation of cyclopropanols 1a-g on air was dramatically depressed, and so intensive bubbling with atmospheric O₂ was required in this case to perform the reaction. The replacement of benzene by the non-flammable chlorinated C₁-hydrocarbons led to the formation of halogen-containing compounds as by-products.