Doubly Stereodifferentiating Hiyama Addition with Mismatched Reactants; Enantio‐ and Diastereo‐controlled Synthesis of Dihydrocanadensolide

Carbon skeleton, functionalization pattern, and chirality centers of the target molecule are formed at once in the key step of the synthesis of 1, a metabolite of Penicillium canadense. This key step is the highly steroselective Hiyama reaction of a chiral allyl bromide derivative with an α-chiral aldehyde in the mismatched combination with predominance of the allyl components.