Various situations are explored in which the nickel (0)-catalyzed enyne–epoxide reductive coupling was utilized to access key intermediates toward the total synthesis of (−)-cyatha-3, 12-diene (1). Enantioenriched 3, 5-dien-1-ols with a variety of functionality were obtained in a straightforward manner from easily accessible 1, 3-enynes and terminal epoxides.