A Palladium‐Catalyzed Decarboxylative Heck‐Type Reaction of Disubstituted Vinylphosphonates in the Stereoselective Synthesis of Trisubstituted Vinylphosphonates

We describe a highly stereoselective and atomically economical approach for the preparation of trisubstituted vinylphosphonates through palladium‐catalyzed decarboxylative Heck‐type reactions of vinylphosphonates. Excellent E/Z selectivity was achieved mostly with E‐isomers; this was difficult to achieve via traditional methods. Oxygen in the air was the sole oxidant, and this minimizes the use of high‐loading silver or other species. This work is the first example to synthesize vinylphosphonates via a catalyzed decarboxylative Heck‐type reaction. We describe a highly stereoselective and atomically economical approach for the preparation of trisubstituted vinylphosphonates through palladium‐catalyzed decarboxylative Heck‐type reactions of vinylphosphonates. Excellent E/Z selectivity was achieved mostly with E‐isomers with oxygen in the air was the sole oxidant; this was difficult to achieve via traditional methods. This work is the first example to synthesize vinylphosphonates via a catalyzed decarboxylative Heck‐type reaction.