The reaction of epoxides with strong base constitutes well-known synthetic methods for the preparation of allylic alcohols. Because of our needs to carry out such transformation under very mild condition, we developed a new method based upon diethylaluminum dialkylamide. The method takes advantages of the affinity of aluminum metal for oxygen. Diethylaluminum tetramethylpiperidide (DATMP) has proved to be most satisfactory for the above isomerization, and several epoxides are converted to the corresponding allylic alcohols in high yields with high regio- and stereospecificities at 0°for 2-3 hr. Thus, the Z-epoxide 3 gives the disubstituted allylic alcohol 4, while the E isomer transforms to the alcohol 6. General synthetic method for the conversion of allylic alcohols to diene compounds with high specificity is enunciated. The method depends heavily on the application of DATMP promoted oxirane rearrangement described above. Myrcene, trans-ocimene, β-, and α-farnesene are synthesized from their biological precursor, nerol, geraniol, cis-, and trans-farnesol, respectively.