Réka Henyecz and György Keglevich* Pages 523 - 545 ( 23 )
Background: The Hirao reaction discovered ca. 35 years ago is an important P–C coupling protocol between dialkyl phosphites and aryl halides in the presence of Pd(PPh3)4 as the catalyst and a base to provide aryl phosphonates. Then, the reaction was extended to other Preagents, such as secondary phosphine oxides and H-phosphinates and to other aryl and hetaryl derivatives to afford also phosphinic esters and tertiary phosphine oxides. Instead of the Pd(PPh3)4 catalyst, Pd(OAc)2 and Ni-salts were also applied as catalyst precursors together with a number of mono- and bidentate P-ligands.
Objective: In our review, we undertook to summarize the target reaction with a special stress on the developments attained in the last 6 years, hence this paper is an update of our earlier reviews in a similar topic.
Conclusions: “Greener” syntheses aimed at utilizing phase transfer catalytic and microwave-assisted approaches, even under “P-ligand-free. or even solvent-free conditions are the up-to date versions of the classical Hirao reaction. The mechanism of the reaction is also in the focus these days.
Hirao reaction, P-C coupling, Pd-catalyst, phosphonates, phosphinates, phosphine oxides, green synthesis.
Department of Organic Chemistry and Technology, Budapest University of Technology and Economics, 1521 Budapest, Department of Organic Chemistry and Technology, Budapest University of Technology and Economics, 1521 Budapest