New Applications of the Allylic Diazene Rearrangement

by Shrestha, Maha L.; Qi, Wei; Matt, McIntosh

We have recently reported diastereoselective reductive 1,3-transpositions of acyclic a,a-unsatd. tosyl hydrazones to afford substrates with a 1,4-syn or 1,4-anti relationship between alkoxy and Me groups. In these reports, trisubstituted alkenes (R= H) were employed. We are currently engaged in examg. tetrasubstituted alkenes (R=Me) in trisubstitued E-alkenes. Such stereochem. arrays are frequently obsd. in marine natural products such as tedanolide.