Ruthenium complex catalyzed benzylation of arenes with benzyl formates; decarbonylation and decarboxylation of alkyl formates

doi:10.1016/S0040-4039(00)99342-0

Tetrahedron Letters

Volume 30, Issue 31, 1989, Pages 4137-4140

https://doi.org/10.1016/S0040-4039(00)99342-0 Get rights and content

Abstract

Ru₃(CO)₁₂-(CH₃)₃NO·2H₂O showed high catalytic activity for the decarbonylation of alkyl formates to the corresponding alcohols at 150 – 200 °C under an argon atmosphere. Decarbonylation of β-phenetyl formate afforded β-phenetyl alcohol in 82 % yield. On the other hand, when decarbonylation of benzyl formate was performed in the absence of (CH₃)₃NO·2H₂O, benzylation of arenes, which were employed as a solvent, proceeded via catalytic decarboxylation of benzyl formate. For the reaction of toluene with benzyl formate, phenyltolylmethane (o-, m-, and p-mixture) was obtained in total 77 % yield.

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References (12)

J.S. Matthews et al.
J. Org. Chem.
(1970)
M.R. Sandner et al.
J. Org. Chem.
(1973)
H.A. Zahalka et al.
Organometallics
(1986)
H.A. Zahalka et al.
Tetrahedron Lett.
(1987)
G. Doyle
Chem. Abstr.
(1982)
Y. Watanabe et al.
J. Org. Chem.
(1984)
K. Weissermel et al.
(1978)
T. Hiratani et al.
CEER, Chem. Econ. Eng. Rev.
(1985)
R.L. Pruett et al.
Organometallics
(1982)
C. Buchan et al.
J. Chem. Soc., Chem. Commun.
(1986)

There are more references available in the full text version of this article.

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Ruthenium complex catalyzed benzylation of arenes with benzyl formates; decarbonylation and decarboxylation of alkyl formates

Abstract

J. Org. Chem.

J. Org. Chem.

Organometallics

Tetrahedron Lett.

Chem. Abstr.

J. Org. Chem.

CEER, Chem. Econ. Eng. Rev.

Organometallics

J. Chem. Soc., Chem. Commun.