Saegusa oxidation reaction

SAE reaction see Sharpless asymmetric epoxidation Saegusa oxidation 390 samarium diiodide 496, 633, 638 saponification 49, 207 sativene 382 f. 

The Larock modified Saegusa oxidation conditions were utilized in the total synthesis of ( )-8,14-cedranoxide by M. lhara et al. The main strategy was to apply an intramolecular double Michael addition reaction to assemble the tricyclic cedranoid skeleton. The precursor five-membered enone was prepared in high yield from the corresponding substituted cyclopentanone in two steps. 

Transition metal enolate complexes have been prepared with most or all transition metals, and the enolate ligands have been shown to adopt a variety of bonding modes. Bofli early and late transition metal enolate complexes are intermediates in a number of important catalytic processes. Early transition metal enolates are important intermediates in asymmetric aldol reactions that exploit the Lewis acidic character of early metals. Late transition metal enolates are intermediates in aldol and Michael addition processes, -Saegusa oxidations,Heck-type processes, catalytic asymmetric conjugate additions, - and cross coupling of enolate nucleophiles. - ... 

The first case of a tetrahedral palladium(O) tetraolefin complex (more exactly, Pd(diolefin)2) has been isolated in the course of the Saegusa oxidation of a silyl enol ether, aimed at the synthesis of alkaloids. Palladium acetate was used as oxidant in this reaction, and a brown compound separated from the solution, which was characterized by X-ray diffraction as 16 (Equation (5)). It decomposed upon heating to give the expected product of oxidation. This supports the accepted mechanism of Saegusa oxidation. ... 

The first total synthesis of the marine polycyclic ether toxin (-)-gambierol was accomplished in the laboratory of M. Sasaki. The introduction of the a,(3-unsaturation into the seven-membered H ring of the FGH tricyclic subunit proved to be problematic, because both the conventional selenium-based method and the Nicolaou oxidation with IBX failed. However, when the seven-membered ketone was treated with LiHMDS in the presence of TMSCI and EtsN, the corresponding silyl enol ether was formed, which was oxidized under Saegusa conditions to give the desired cyclic enone in high yield. Because of the small scale of the reaction, a large excess of Pd(OAc)2 was used in acetonitrile so the presence of a co-oxidant was not necessary. 

The oxidation of trimethylsilylenol ethers under Wacker-type conditions gives rise to a,P-unsaturated ketones (Experimental Procedure below). This reaction was discovered by Saegusa and Ito and bears their names. The selectivity for the oxidation of unmodified ketones is somewhat lower. ... 

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