Metallo-phosphorylation of alkenes: a highly regioselective reaction of zirconocene–alkene complexes with chlorophosphate

Regioselective Zirconophosphination of 1-Alkenes: A Versatile Route for the Synthesis of β-Functionalized Alkyldiphenylphosphine Oxides in the Presence of CuCl

“…The zirconocene-mediated synthesis of different organophosphorus compounds has been demonstrated. – We have previously reported that zirconophosphorylation of C−C multiple bonds afford various organophosphonates RP(O)(OR) 2 . Recently, reaction of alkynes with Cp 2 Zr species and chlorodiphenylphosphine to afford zirconoalkenylphosphines in high yields has been demonstrated .…”

In Situ Generation of Phosphoryl Alkylindiums and Their Synthetic Application to Arylalkyl Phosphonates via Palladium-Catalyzed Cross-Coupling Reactions

“…Because 2-aryl phosphonate derivatives have been known to be inhibitors of the human low molecular weight protein tyrosine phosphatase (HCPTP), 6 synthesis of these compounds from easily accessible precursors has been continuously investigated (Scheme 1): Cu-catalyzed synthesis of alkylphosphonates from H-phosphonates and N-tosylhydrozones (a), 7 the reductive deoxygenation of acyl phosphonates (b), 8 reaction of phosphorus-containing carbenoids with organoboranes (c), 9 Cs 2 CO 3 -promoted synthesis of phosphonates (d), 10 and reaction of zirconocene−alkene complexes with chlorophosphate (e). 11 As shown in Scheme 1, all of these reactions were achieved via the formation of the P−C (sp 3 ) bond. In contrast, Takagi and co-workers recently reported a Rh-catalyzed crosscoupling reaction of arylzinc reagent with 2-iodoethyl phosphonate, leading to 2-aryl phosphonates via the formation of a C−C bond (f).…”