Reaction of oxazirconacycloheptenes with aldehydes mediated by CuCl: one-pot synthesis of tetrahydrofuran derivatives from four different components involving two molecules of the same or different aldehydes, an ethylene and an alkyne

Abstract

Reaction of zirconacyclopentenes with 2 equiv. of the same aldehydes in the presence of 1 equiv. of CuCl from −78 °C to room temperature afforded tetrahydrofuran derivatives in good isolated yields upon hydrolysis with aqueous 3 N HCl. Oxazirconacycloheptenes, generated in situ from zirconacyclopentenes with one aldehyde was found to be the reactive intermediate. When treated with a second aldehyde and CuCl, an oxazirconacycloheptene gave a tetrahydrofuran derivative comprised of four different components involving an alkyne, an ethylene and two different aldehydes, thus providing the first one-pot synthesis of important tetrahydrofuran derivatives from four components. When bulky aldehydes were used, hydrolysis of the above reaction mixtures afforded 2-hexen-1,6-diols, which could be quantitatively transformed to their corresponding tetrahydrofuran derivatives when treated with stronger aqueous acid (12 N HCl).