Palladium/Nickel-catalyzed Phosphonylation Of 2,3-allenols

Phosphorus chemistry is closely related to life science.The construction of various kinds of organophosphorus compounds is a fundamental and significant topic in modern synthetic chemistry due to their broad applicability in biochemistry,pharmaceuticals,material science and organic synthesis.Therefore,the development of new and economic methodologies for efficient access to organophosphorus compounds with diverse structures is still desired.In recent years,allene chemistry has been developed rapidly,and the synthesis method of allene is more convenient,resulting that 2,3-allenol has attracted scientists’ attention as an effective reaction precursor due to its unique reaction features.This paper focused on carrying out new methods for the construction of unique organophosphorus compounds using 2,3-allenols and different P(O)H compounds,mainly including two parts:The first part introduces a facile and efficient palladium-catalyzed direct C-P cross-coupling of various unprotected 2,3-allenol with readily available Hphosphonates to access a large variety of structurally diverse multisubstituted 2phosphinoyl-1,3-butadienes in one pot.The reaction features operational simplicity,excellent regioselectivity,high step-and atom-economy and moderate to excellent yields.The second part introduces a unique nickel-based catalytic system to produce the corresponding 3-alkenyl-1,2-bisphosphoryl compounds in moderate to excellent yields.A simple one-pot access to 3-alkenyl-1,2-bisphosphoryl compounds was demonstrated using 4-(ethoxycarbonyl)-2,3-alcohol as starting materials.The salient features of this protocol included the excellent stereoselectivity for E stereoisomers,operational simplicity,remarkable functional group tolerance and moderate to excellent yields.