METAL-AMMONIA REDUCTION OF ETHERS OF 3-DECYN-1-OL - EFFECTS OF STRUCTURE AND CONDITIONS ON CLEAVAGE AND REARRANGEMENT

Reduction of the THP, ethyl, tert-butyl and tert-butyldimethylsilyl (T BDMS) ethers of 3-decyn-1-ol with sodium in ammonia/THF results in ext ensive hydrogenolysis of the carbon-oxygen bond and concomitant bond m igration, producing a mixture of 2- and 3-decenes and a very low yield of the desired (E)-homoallylic ether. Reduction in the presence of 2- methyl-2-propanol led to excellent yields of the desired (E)-3-decenol ethers. The 4- and 5-decyn-1-ol ethers were reduced normally to the ( E)-decen-1-ol ethers except in the case of the TBDMS ethers which were cleaved to the (E)-alcohols under some of the reaction conditions.