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Synfacts 2022; 18(11): 1221
DOI: 10.1055/s-0042-1753012
Metals in Synthesis

The Hirao Reaction: Palladium-Catalyzed Cross-Coupling of Dialkyl Phosphites with Aryl Halides

Contributor(s):
Martin Oestreich
,
Hendrik F. T. Klare
,
Phillip Pommerening
Hirao T, *, Masunaga T, Ohshiro Y, Agawa T. Osaka University, Japan
A Novel Synthesis of Dialkyl Arenephosphonates.

Synthesis 1981; 56-57
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Key words

C(sp2)–P bond formation - palladium catalysis - phosphonates

Significance

In 1981, Hirao and co-workers disclosed the direct cross-coupling of aryl halides with dialkyl phosphites in the presence of a palladium(0) catalyst and an amine base to give the corresponding aryl phosphonates. In contrast to the Michaelis–Arbuzov reaction, this protocol enables the facile formation of C(sp2)–P bonds.


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Comment

While most products were isolated in good to excellent yields, the cross-couplings of para-hydroxyphenyl and para-aminophenyl halides were ineffective. The substrate scope was successfully extended to vinyl halides (Tetrahedron Lett. 1980, 21, 3595), affording the corresponding vinyl phosphonates in high yields (see grey box).


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Publication History

Article published online:
18 October 2022

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