Rubottom oxidation

Rubottom oxidation
Named after George M. Rubottom
Reaction type Organic redox reaction
Identifiers
Organic Chemistry Portal rubottom-oxidation

The Rubottom oxidation is a useful, high-yielding chemical reaction between silyl enol ethers and peroxyacids to give the corresponding α-hydroxy carbonyl product.[1][2][3][4][5] The mechanism of the reaction was proposed in its original disclosure by A.G. Brook[6][7] with further evidence later supplied by George M. Rubottom.[8] After a Prilezhaev-type oxidation of the silyl enol ether with the peroxyacid to form the siloxy oxirane intermediate, acid-catalyzed ring-opening yields an oxocarbenium ion.[1][4] This intermediate then participates in a 1,4-silyl migration (Brook rearrangement) to give an α-siloxy carbonyl derivative that can be readily converted to the α-hydroxy carbonyl compound in the presence of acid, base, or a fluoride source.[1][9][10]

  1. ^ a b c Kürti, pp. 388–389.
  2. ^ Myers, A.G. Chemistry 215: Oxidation Archived 2011-03-12 at the Wayback Machine. chem.harvard.edu
  3. ^ Christoffers, J.; Baro, A.; Werner, T. (2004). "α-Hydroxylation Of β-Dicarbonyl Compounds". Adv. Synth. Catal. 346 (23): 143–151. doi:10.1002/adsc.200303140.
  4. ^ a b Li, pp. 478–479.
  5. ^ Chen, B. C.; Zhou, P.; Davis, F. A.; Ciganek, E. (2003) “α-Hydroxylation of Enolates and Silyl Enol Ethers." in Organic Reactions; Ed. Overman, L.E. Wiley, Chapter 1, pp. 1–355, doi:10.1002/0471264180.or062.01.
  6. ^ Brook, A. G.; Macrae, D. M. (1974). "1, 4-Silyl Rearrangements of Siloxyalkenes to Siloxyketones During Peroxidation". J. Organomet. Chem. 77 (2): C19–C21. doi:10.1016/S0022-328X(00)81332-7.
  7. ^ Brook, A. G. (1974). "Molecular Rearrangements of Organosilicon Compounds". Acc. Chem. Res. 7 (3): 77–84. doi:10.1021/ar50075a003.
  8. ^ Rubottom, G. M.; Gruber, J. M.; Boeckman, R. K. Jr; Ramaiah, M.; Medwid, J. B. (1978). "Clarification of the Mechanism of Rearrangement of Enol Silyl Ether Epoxides". Tetrahedron Lett. 19 (47): 4603–4606. doi:10.1016/S0040-4039(01)85682-3.
  9. ^ Myers, A.G. Chemistry 215: Protective Groups-Silicon-Based Protection of the Hydroxyl Group. chem.harvard.edu
  10. ^ Kocieński, P.J. (2005) Protecting Groups. 3rd Edition, Thieme, pp. 188–230, ISBN 1588903761.