Sarett’s reagent

Lead tetraacetate oxidation (63) of oxodelcosine (LXXXV) gave LXXXVII, presumably arising from the expected diketone LXXXVI. Evidence favoring structure LXXXVII was the further oxidation of one of the two hydroxyls to a five-membered ketone (LXXXVIII) with Sarett s reagent. Thus, the unreacted hydroxyl of LXXXVII must be tertiary this can be explained if the C-1 hydroxyl reacted with the C-8 ketone to form a hemiketal. Furthermore, the hemiketal formation as... 

An attempt to correlate delcosine with lycoctonine proved to be a failure (63), but it did show that the C-6 position of delcosine is substituted with a methoxyl group, a fact previously unestablished and assumed only by analogy with lycoctonine. The initial reactions involved an epimerization at C-1 since lycoctonine has a j8-methoxyl at C-1. This was accomplished by first oxidizing A-desethyldelcosine (XCIII) with Sarett s reagent, giving a mixture of the azomethine XCIV and the diketo lactam XCV. Ethylation of the azomethine (XCIV) was followed... 

Oxidation of browniine (CVIII) with Sarett s reagent gave dehydro-oxobrowniine (CIX), which was a cyclic five-membered monoketo lactam. 

Another reaction which indicated that the CD ring structure of aconitine is similar to that of delphinine was the oxidation of oxonine (CXXXVIII), the hydrolysis product of oxonitine (CXXXIII), with Sarett s reagent to obtain the rearranged diketone CXL. The latter is assumed to arise from a base-catalyzed acyloin rearrangement of the original oxidation product (CXXXIX) which was not isolated. 

Oxidation with Sarett s reagent gave two products (1) the azomethine CCXCVIII which formed the ethiodide CCXCIX, convertible to chasmanine by reduction with sodium borohydride, and (2) the neutral V-acetyl-A-desethyl-14-dehydrochasmanine (CCC). The stereospecific course of the reduction of the five-membered ketone is indicative of the ketone carbonyl being at C-14 rather than C-12 and is consistent with the stereochemistry of these skeletons which have free access to the C-12 position, whereas the C-14 position is hindered by ring D, leaving only one side open for attack. 

Oxidation of heteratisine acetate with Sarett s reagent gives three products, 19-oxoheteratisine acetate (20) in a yield of 70—75%, iV-desethyl-19-oxohetera-tisine acetate (21), and the azomethine (22). Treatment of heteratisine and oxoheteratisine with chromium trioxide in acetic acid yields dehydroheteratisine (23) and oxodehydroheteratisine (24), respectively. Comparison of their i.r. 

Grignard reaction with formaldehyde closer to our desired product. Subsequent hydrolysis will yield 2,2-dimethylbutanol our desired product is 2,2-dimethylbutanal. Oxidation of the primary alcohol to the aldehyde can be accomplished with Sarett s reagent, a combination of chromium trioxide (CrOs) with pyridine. 

NMR spectra in the presence of Eu(FOD)3 shift reagent. Oxidation of the isomeric dihydromyliols by Sarett s reagent gave dihydromylione A (43) and dihydromylione B (83). The spectral data of natural dihydromylione were identical with those of dihydromylione A. Acid treatment of myliol (44) also yielded dihydromylione A (43). 

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