Saegusa- Ito oxidation

By Saegusa-Ito oxidation " Dehydrosilylation of silyl enol ethers with... 

Palladium-catalyzed conversion of enol silanes to enones, also known as the Saegusa enone synthesis or the Saegusa-Ito oxidation. 

After the known intermediate 79 (contaminated with ca. 6 % < /.v isomer) [39] was prepared from Hajos-Parrish ketone [40] 78, the tert-butyl ether was cleaved (quant.) and the ketone protected as the acetal (96 %). The secondary alcohol was oxidized by pyridinium chlorochromate (PCC) to provide ketone 80 in good yield (71 %) and after fractional crystallization afforded material absent of any m-hydrindane (Scheme 10.6). [NOTE All compounds shown in Schemes 10.6 and 10.7 are shown in the ent-configuration, as published]. The oxidation of protected hydrindane 80 under Saegusa-Ito conditions [41, 42] gave enone 81 (82 %), confirmed by X-ray crystallography. 

Then 44 was converted into ketone 45 by the conventional hydroboration-oxidation procedure and the subsequent Dess-Martin oxidation (Scheme 9). At this stage. X-ray crystallographic analysis of 45 enabled us to determine the configuration of the stereogenic center at C-4 as (5). By applying the Ito—Saegusa... 

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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