Second generation alpha-enones from a pyranosidic alpha-enone.
The Diels-Alder product from the reaction of methyl 2,3,6-trideoxy-alpha-D-glycero-hex-2-enopyranosid-4-ulose (1b) with trans-1-methoxy-3-tert-butyl-dimethylsilyloxy-1,3-butadiene is 3b (93%). Reaction of 3b wih sodium borohydride causes reduction of the C-4 carbonyl group only, but, with lithium aluminum hydride, further reactions occur which can be rationalized by fragmentation brought about by hydride cleavage on the silicon-oxygen bond, with simultaneous ejection of the beta-methoxyl group complexed to a trivalent aluminum species. The enone resulting from this fragmentation also reacts further with lithium aluminum hydride, and several products result. The behavior of postulated intermediates, which have been prepared separately and subjected to the reaction conditions, supports the proposed reaction mechanisms. The "second generation" enone (methyl 2,3,6-trideoxy-alpha-D-talopyranosido)-[3,2-d]-2-cyclohexenone+ ++ (10a), arising from the first generation precursors 1b, has been prepare by two routes.
D055598:Chemical Phenomena; D002621:Chemistry; D006863:Hydrogen-Ion Concentration; D009682:Magnetic Resonance Spectroscopy; D008759:Methylglycosides; D013237:Stereoisomerism
D008759:Methylglycosides; C045833:methyl 2,3,6-trideoxy-alpha-glycero-hex-2-enopyranosid-4-ulose; C045834:(methyl 2,3,6-trideoxy-alpha-talopyranosido)-(3,2-d)-2-cyclohexanone