Pd-catalyzed highly regio-, diastereo-, and enantioselective allylic alkylation of α-fluorophosphonates

Highly efficient Pd-catalyzed asymmetric allylic alkylation reaction of ethyl-2-fluoro-2-(diethoxyphosphoryl)acetate with monosubstituted allylic substrates has been developed, affording corresponding α-fluorophosphonates with two chiral centers in high regio-, diastereo- and enantio-selectivities. The usefulness of the products in organic synthesis has been demonstrated.!divAbstract

Double Role of the Hydroxy Group of phosphoryl in Palladium(II)-catalyzed ortho-Olefination: A Combined Experimental and Theoretical Investigation

Density functional theory (DFT) calculations have been carried out on Pd-catalyzed phosphoryl-directed ortho-olefination to probe the origin of the significant reactivity difference between methyl hydrogen benzylphosphonates and dialkyl benzylphosphonates. The overall catalytic cycle is found to include four basic steps: C−H bond activation, transmetalation, reductive elimination and recycling of catalyst, each of which is constituted from different steps.

Insertion reactions of allenes with palladium aryl complexes [PdI(Ph)(PPh3)](2) and PdI(Ph)(dppe)

Treatment of [PdI(Ph)(PPh3)]2 with allenes CH2═C═CHR (R = CMe3, CO2Et, P(O)(OEt)2, and SO2Ph) in dichloromethane at room temperature produces a mixture of cis and trans isomers of the π-allyl palladium complexes PdI(η3-CH2C(Ph)CHR)(PPh3) in which the R group is anti to the Ph group. The disubstituted allenes MeCH═C═CHR (R = P(O)(OEt)2 and SO2Ph) similarly react with [PdI(Ph)(PPh3)]2 to give the π-allyl palladium complexes PdI(η3-MeCHC(Ph)CHR)(PPh3) in which the R group is anti and the Me group is syn to the Ph group.