Silaborative Assembly of Allenamides and Alkynes: Highly Regio- and Stereocontrolled Access to Bi- or Trimetallic Skipped Dienes

A highly stereo- and regiocontrolled multicomponent approach to skipped 1,4-dienes decorated with one boryl and two silyl functionalities is described. This Pd-catalyzed atom-economical union of allenamides, alkynes, and Me(2)PhSiBpin (or Et(3)SiBpin) proceeds without the use of phosphine ligands, instead relying on chelation through the internal amide group of the allenamide sulfonyl. A variety of alkynes, including those derived from complex bioactive molecules, can be efficiently coupled with allenamides and Me(2)PhSiBpin in good yields and with excellent selectivity. The synthetic potential was demonstrated through multiple valuable chemoselective transformations, establishing new disconnections for functionalized dienes. Density functional theory calculations revealed that the reaction first proceeded through borylation of the allenamide, followed by silylation of the alkyne and then reductive elimination, which convergently assemble the skipped 1,4-diene.

Automated summary

This article describes a highly stereo- and regiocontrolled multicomponent approach for the synthesis of skipped 1,4-dienes decorated with one boryl and two silyl functionalities. The advantages of this method include atom-economy, efficient coupling, and excellent selectivity, and it has been demonstrated to be applicable for various valuable chemical transformations.