Rhenium-Catalyzed Epoxide Deoxygenation: Scope and Limitations

Abstract

Transfer of oxygen atoms from epoxides to triphenyl­phosphine is efficiently catalyzed by Tp′ReO₃ [Tp′ = hydrido-tris-(3,5-dimethylpyrazolyl)borate] in benzene at 75-105 ºC. The reaction tolerates a wide variety of functional groups including ketones (conjugated or non-conjugated to the new double bond), esters, nitriles, ethers, silyl ethers and phthalimides. Relative rates vary with substitution pattern and electronics; in general, monosub­stituted and 2,2-disubstituted epoxides react fastest, and cis-2,3-di­substituted systems react faster than trans. Electron-withdrawing substituents promote the reaction.

Key words

epoxide deoxygenation - rhenium catalysis - O-atom transfer

References

• 1 Gable KP. Brown EC. Organometallics  2000,  19:  944 
• 2a Kraus GA. Thomas PJ. J. Org. Chem.  1988,  53:  1395 
• 2b Johnson WS. Plummer MS. Pulla Reddy S. Bartlett WR. J. Am. Chem. Soc.  1993,  115:  515 
• 3 Carbohydrates as Organic Raw Materials II   Descotes G. VCH; New York: 1993. 
• 4a Wittig G. Haag W. Chem. Ber.  1955,  88:  1654 
• 4b Vedejs E. Fuchs PL. J. Am. Chem. Soc.  1973,  95:  822 
• 4c Tamagaki S. Sakaki K. Oae S. Bull. Chem. Soc. Jpn.  1972,  45:  3179 
• 4d Yamada K. Goto S. Nagase H. Kyotani Y. Hirata Y. J. Org. Chem.  1978,  43:  2076 
• 4e Suzuki H. Fuchita T. Iwasa A. Mishina T. Synthesis  1978,  905 
• 5a Reetz MT. Plachky M. Synthesis  1976,  199 
• 5b Denis JN. Magnane R. Van Eenoo M. Krief A. Nouv. J. Chim.  1979,  3:  705 
• 5c Caputo R. Mangoni L. Neri O. Palumbo G. Tetrahedron Lett.  1981,  22:  3551 
• 5d Mangette JE. Powell DR. West R. J. Chem. Soc., Chem. Commun.  1993,  1348 
• 5e Mangette JE. Powell DR. Calabrese JC. West R. Organometallics  1995,  14:  4064 
• 5f Mangette JE. Powell DR. Firman TK. West R. J. Organomet. Chem.  1996,  521:  363 
• 6a Calo V. Lopez L. Mincuzzi A. Pesce G. Synthesis  1976,  200 
• 6b Ogawa A. Miyake J. Murai S. Sonoda N. Tetrahedron Lett.  1985,  26:  669 
• 6c Dittmer DC. Zhang Y. Discordia RP. J. Org. Chem.  1994,  59:  1004 
• 7a Rosenblum M. Saidi MR. Madhavarao M. Tetrahedron Lett.  1975,  16:  4009 
• 7b Alper H. Des Roches D. Tetrahedron Lett.  1977,  18:  4155 
• 7c Hayasi Y. Schwartz J. Inorg. Chem.  1981,  20:  3473 
• 7d Umbreit MA. Sharpless KB. Org. Synth.  1981,  60:  29 
• 7e Sato M. Oshima K. Chem. Lett.  1982,  157 
• 7f Miyata N. Santa T. Hirobe M. Chem. Pharm. Bull.  1984,  32:  377 
• 7g Moloy KG. Inorg. Chem.  1988,  27:  677 
• 7h Sarmah P. Barua NC. Tetrahedron Lett.  1988,  29:  5815 
• 7i Chowdhury PK. J. Chem. Res., Synop.  1990,  192 
• 7j Whinnery LL. Henling LM. Bercaw JE. J. Am. Chem. Soc.  1991,  113:  7575 
• 7k Mitchell PWD. Org. Prep. Proced., Int.  1990,  22:  534 
• 7l Isobe H. Branchaud BP. Tetrahedron Lett.  1999,  40:  8747 
• 8 Arterburn JB. Liu M. Perry MC. Helv. Chim. Acta  2002,  85:  3225 
• 9 Gable KP. Brown EC. J. Am. Chem. Soc.  2003,  125:  11018 
• 10a Herrmann WA. Ding H. Kühn FE. Scherer W. Organometallics  1998,  17:  2751 
• 10b Romão CC. Kühn FE. Herrmann WA. Chem. Rev.  1997,  97:  3197 
• 11 Holm RH. Donahue JP. Polyhedron  1993,  12:  571 
• Tp′ReO₃ was prepared by the method of Mayer, et al.:
• 13a Matano Y. Northcutt TO. Brugman J. Bennett BK. Lovell S. Mayer JM. Organometallics  2000,  19:  2781 
• 13b

  In this method Re₂O₇ reacted with 2 equivalents trifluoroacetic anhydride in THF, followed by addition of KTp′. The solid trioxo complex precipitates and is collected by filtration and washed.

12

After 4 h, a trace of alkene was observed. However, the major product was reaction of the carbonyl oxygen to form 2-methyl-5-hydroxymethyloxazoline.