3-Octalone catalytic

Three independent syntheses of fukinone (335) have been published. In the first of these, Piers and Smillie ° converted the octalone (336), which they had previously used in connection with their synthesis of aristolone, into (337) by treatment with ethyl formate followed by catalytic reduction. Dehydrogenation of (337) with 2,3-dichloro-5,6-dicyanobenzoquinone and subsequent oxidation and esterification yielded (338). This keto-ester was converted into fukinone (335) by hydrogenation followed by methylation of the enolate ester and dehydration of the resultant keto-alcohol (339). Torrence and Finder have also completed the synthesis of fukinone using the octalone (336) as the key intermediate. 

The catalytic reactions of polar groups is influenced by the polarity of the solvent. The hydrogenation of A >9-octalone-2 (13) produces both the cis (14) and trans (15) p decalones (Eqn. 5.3). As shown by the data in Table 5.1, in aprotic... 

The continued fascination chemists possess with asymmetric synthesis provides the basis for the next four procedures. The synthesis of (R)-(-)-10-METHYL-l(9)-OCTALONE-2 is a nice demonstration of an asymmetric Michael addition by a chiral imine followed by an aldol—in short an asymmetric Robinson annulation. The asymmetric glycolization to STILBENE DIOL (R,R-l,2-DIPHENYL-I,2-ETHANEDIOL) represents an olefin oxidation using catalytic alkaloids in tandem with osmium tetroxide. As reagents for a variety of asymmetric alkylations, the preparation of 2-CYANO-6-PHENYLOXAZOLOPIPERIDINK is pavscnicd as well as another route to... 

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