Phosphine-Catalyzed Remote 1,7-Addition for Synthesis of Diene Carboxylates

A phosphine-catalyzed remote 1,7-addition of vinyl allenoates has been developed, providing a series of 1,3-dienes derivatives in high yields (up to 99%) and with good chemo-, regio-, and stereoselectivity. This reaction demonstrated that the introduction of vinyl in allenoates effectively extended reaction types of phosphine-catalyzed nucleophilic addition of allenoates, leading to concise synthesis of diene carboxylates. Notably, the enantioselective variant of this 1,7-addition can also be performed by chiral phosphine catalyst.