Novel routes to Lamisil via hydroboration followed by Suzuki coupling

ORGN 631

Narayan G. Bhat, nbhat@panam.edu and Joshua D. Gracia. Department of Chemistry, University of Texas-Pan American, 1201 West University Drive, Edinburg, TX 78541
A highly diastereoselective synthesis of Lamisil, an antifungal agent is developed. Two methods are explored based on the hydroboration and Suzuki coupling reactions. In the first method, the starting propargylamine containing a naphthylmethyl group is hydroborated with dichloroborane-dioxane complex followed by treatment with 1,3-propanediol. The resulting (E)-alkenylboronate ester is coupled with 1-bromo-3,3-dimethyl-1-butyne in the presence of Pd(0) catalyst and sodium methoxide in methanol to provide Lamisil in 72% isolated yield. The second method involves the hydroboration of propargyl chloride with dichloroborane-dioxane complex followed by a reaction with 1,3-propanediol. It is then converted into an “ate” complex with lithium isopropoxide. The resulting “ate” complex is reacted with lithiated methyl naphthylmethyl amine to undergo a substitution product containing an (E)-double bond and a boronate moiety. It is then subjected to Suzuki coupling using a Pd(0) catalyst, a base, and 1-bromo-3,3-dimethyl-1-butyne to provide Lamisil in 74% isolated yield. In both methods, the reaction proceeds to yield Lamisil in high stereochemical purity.