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.

The first enantioselective sequential phosphine-catalyzed (SPC as abbreviation) mode for the formation of tetrahydroquinolines with an ethynyl-substituted all-carbon quaternary stereogenic center is reported. In this SPC process, a novel [4 + 2] annulation process was devised employing α-substituted allenoates as C2 synthons (α–β′, 1,2-dipole) for the first time. 3-Ethynyl-substituted tetrahydroquinolines were readily prepared in good yields and high enantioselectivities.

The first (3 + 2)/(3 + 2) sequential annulation of γ-vinyl allenoates with alkylidenemalononitriles enabled by phosphine catalysis has been reported. A broad range of structurally dense tetra- and penta-substituted bicyclic­[3,3,0]­octene derivatives, containing a quaternary center and three sequential stereogenic center, were synthesized in good to excellent yields. In this approach, three new C–C bonds are formed in one pot, and εC and αC of γ-vinyl allenoate are two electrophilic centers, whereas its γC exhibits nucleophilic reactivity.

A phosphine-catalyzed (3+2)/(2+3) sequential annulation involving a triple nucleophilic addition reaction of γ-vinyl allenoates was successfully developed.