C O M M U N I C A T I O N S
Table 2. Oxidative Heck-Type Reaction of Arylphosphonic Acidsa
provides the intermediate 4. An aryl transfer from phosphorus to
palladium yields arylpalladium species, which then reacts with an
alkene to afford the Heck product 2 and Pd(0) species via
â-elimination. Oxidation of Pd(0) with Me3NO regenerates Pd(II)
species.
In conclusion, we have found that the reaction of arylphosphonic
acids with a variety of alkenes provides the Heck-type adducts in
the presence of a catalytic amount of Pd(OAc)2. The reaction
requires an oxidant and TBAF as the activator and proceeds via
carbon-phosphorus bond cleavage.
Acknowledgment. This work was supported by a Grant-in-Aid
for Scientific Research from the Ministry of Education, Culture,
Sports, Science, and Technology, Japan. A.I. acknowledges JSPS
for financial support.
Supporting Information Available: General procedures (PDF).
This material is available free of charge via the Internet at http://
pubs.acs.org.
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a
The mixture of arylphosphonic acid (0.3 mmol), alkene (0.36 mmol),
Pd(OAc)2 (0.015 mmol), Me3NO‚2H2O (0.9 mmol), TBAF (0.6 mmol, 1
M THF solution), and 1,4-dioxane (3 mL) is stirred at 100 °C for 24 h.b
c
d
(14) An addition of TBAF (1.0 equiv) to a solution of phenylphosphonic acid
Pd(OAc)2 (0.03 mmol) is used. Reaction time is 64 h. Toluene is
employed as a solvent. Diphosphonic acid (0.15 mmol) is used.
e
in 1,4-dioxane causes an upfield shift of a signal by about 10 ppm in 31
P
NMR spectrum. However, no coupling between 31P and 19F could be
observed.
fluoride ion to an arylphosphonic acid generates a pentacoordinated
phosphorus compound 3.13,14 Ligand exchange on palladium
JA026758V
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