Rubottom oxidation

Related reactions Jacobsen-Katsuki epoxidation, Prilezhaev oxidation, Rubottom oxidation, Sharpless asymmetric epoxidation, Shi... 

Rubottom, G. M. Vazquez, M. A. Pelegrina, D. R. Tetrahedron Lett. 1974, 4319. George Rubottom discovered the Rubottom oxidation when he was an assistant professor at the University of Puerto Rico. He is now a grant officer at the National Science Foundation. 

W. S. Trahanovsky (ed.), Oxidation in Organic Chemistry , Academic Press, New York, 1982, vol. SD. Includes charters on (a) Oxidations with Lead(IV) Tetraacetate, by G. M. Rubottom (b) Phase-Transfer Assisted Manganese VU) Oxidation, by D. G. Lee. 

Hegedus and co-workers isolated a cyclobutane-fused epoxide intermediate in the Rubottom oxidation of silyl enol ether 17 (Scheme 9) <1998JOC4691>. 

The highly potent antithrombotic (+)-rishirilide B was synthesized in the laboratory of S.J. Danishefsky. One of the tertiary alcohol functionalities was introduced via the Rubottom oxidation of a six-membered silyl dienol ether with dimethyl dioxirane (DMDO). The oxidation was completely stereoselective, and it was guided by the proximal secondary methyl group. Subsequently, the enone was converted to the enedione, which was used as a dienophile in the key intermoiecuiar Dieis-Aider cycioaddition step. 

The total synthesis of the antitumor antibiotic FR901464 was accomplished by E.N. Jacobsen et al. The preparation of the central six-membered fragment was achieved via a highly enantioseiective hetero Diels-Alder reaction between a diene and an aldehyde. The resulting silyl end ether was subjected to a modified Rubottom oxidation condition (buffer and nonpolar solvent) with mCPBA to afford the desired a-hydroxy ketone with compiete diastereoseiectivity. 

The key step in the total synthesis of the furanoditerpene c/,/-isospongiadiol by P.A. Zoretic and co-workers was an oxidative free-radicai cyciization, which gave rise to the tricyclic skeleton of the natural product.The last stereocenter at C2 was introduced using the Rubottom oxidation on the fully elaborated tetracyclic intermediate. The product was a mixture of a-hydroxy and silyloxy ketone and the last step was a global deprotection with TBAF to afford the natural product. 

In the highly stereoselective synthesis of hispidospermidin, the oxygenation of the CIO position was achieved via a Rubottom oxidation by S.J. Danishefsky et al. The tricyclic ketone was first converted to the TES enol ether, which was readily oxidized with mCPBA to give the corresponding a-hydroxy ketone as a single diastereomer. 

Rubottom oxidation Oxidation of siiyi enoi ethers with mCPBA to giye -hydroxy ketones or -hydroxy aldehydes. 388... 

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