Borylated Cyclopropanes as Spring-Loaded Entities: Access to Vicinal Tertiary and Quaternary Carbon Stereocenters in Acyclic Systems

[Image: see text] Herein, we present the formation of acyclic frameworks bearing two consecutive stereocenters of either tertiary or quaternary nature starting from easily accessible cyclopropenes. This holistic approach involves a regio- and diastereoselective hydro- or carboborylation of substituted cyclopropenyl esters. Formation of boronate complexes of the latter via the addition of nucleophiles and subsequent stereospecific 1,2-migration with carbon–carbon bond cleavage delivered the title compounds.