SYNTHETIC STUDIES ON NOGALAMYCIN: STEREOSPECIFIC C-5 ALKYLATION OF A SUGAR DERIVATIVE VIA CLAISEN REARRANGEMENT AND A NEW ROUTE TO 1,1,4-TRIALKOXYBUTA-1,3-DIENES.

Article abstract of DOI:10.1016/S0040-4020(01)87284-7

Claisen rearrangement of the 4-methoxybutadienylether of the allylic alcohol 13 which was made in 15 steps from D-glucose, afforded one major aldehyde 17 or 18 in good yield.All attempts to oxidize to an acid were unsuccessful.The model compound 24 and compound 13, were converted respectively to the α, β-unsaturated esters 25 and 26.Compound 25 was further transformed into 1,1,4-trialkoxybuta-1,3-diene 27 which was found unreactive towards quinones.