Stereocontrolled Synthesis of Pseurotin A₂

We report synthesis of two diastereomeric structures previously proposed for the complex secondary metabolite pseurotin A₂. Both structures were accessed from the same building blocks taking advantage of a stereodivergent nickel(II)-diamine-catalyzed 1,4-addition of a chiral 2-alkoxycarbonyl-3(2H)-furanone. Late-stage Csp-Csp³ cross-coupling of a highly functionalized bromoalkyne featured in the pseurotin A₂ side-chain assembly. The work supports the 2016 stereochemical revision of pseurotin A₂ and represents the first chemical synthesis of this natural product.