Diastereo- and Enantioselective Access to Stereotriads through a Flexible Coupling of Substituted Aldehydes and Alkenes

: A flexible redox-neutral coupling of aldehydes and alkenes enables rapid access to stereotriads starting from a single stereocenter with perfect levels of enantio- and diastereoselectivity under mild conditions. The versatility of the method is highlighted by the installation of heteroatoms along the tether, which enables a route to structurally diverse building blocks. The formal synthesis of (+)-neopeltolide further demonstrates the synthetic utility of this approach.