Oxidative addition of aryl and benzyl trifluoroacetates to zerovalent palladium complexes with two modes of C-O bond cleavage processes

Kazuhiro Nagayama; Isao Shimizu; Akio Yamamoto

doi:10.1246/bcsj.72.799

Oxidative addition of aryl and benzyl trifluoroacetates to zerovalent palladium complexes with two modes of C-O bond cleavage processes

Kazuhiro Nagayama, Isao Shimizu, Akio Yamamoto^*

^*Corresponding author for this work

Waseda University

Research output: Contribution to journal › Article › peer-review

43 Citations (Scopus)

Abstract

The aryl trifluoroacetates oxidatively added to a zerovalent palladium complex 2a with acyl-O bond cleavage under mild conditions to give the corresponding trans-(aryloxo)(trifluoroacetyl)palladium complexes 3a-3c. But 4-nitrophenyl trifluoroacetate reacted with 2a to yield cis-[Pd(OC₆H₄-4- NO₂)₂(PMe₃)₂] 3d, which was produced with C-O bond activation followed by disproportionation reaction. In contrast, benzyl trifluoroacetates reacted with the Pd(0) complex with benzyl-O bond fission to form benzyl(trifluoroacetato)palladium complexes 4a-4d. Complexes 4a-4d are in equilibrium in solutions between trans and cis isomers, with the proportion of the cis isomer increasing in polar solvents. Palladium-catalyzed carbonylation of benzyl trifluoroacetate has been achieved in the presence of benzyl alcohol arid triethylamine to yield benzyl phenylacetate.

Original language	English
Pages (from-to)	799-803
Number of pages	5
Journal	Bulletin of the Chemical Society of Japan
Volume	72
Issue number	4
DOIs	https://doi.org/10.1246/bcsj.72.799
Publication status	Published - 1999 Apr

ASJC Scopus subject areas

Chemistry(all)

Access to Document

10.1246/bcsj.72.799

Cite this

@article{8cd0d0ed2eac4d3eabe35694acd1aaef,

title = "Oxidative addition of aryl and benzyl trifluoroacetates to zerovalent palladium complexes with two modes of C-O bond cleavage processes",

abstract = "The aryl trifluoroacetates oxidatively added to a zerovalent palladium complex 2a with acyl-O bond cleavage under mild conditions to give the corresponding trans-(aryloxo)(trifluoroacetyl)palladium complexes 3a-3c. But 4-nitrophenyl trifluoroacetate reacted with 2a to yield cis-[Pd(OC6H4-4- NO2)2(PMe3)2] 3d, which was produced with C-O bond activation followed by disproportionation reaction. In contrast, benzyl trifluoroacetates reacted with the Pd(0) complex with benzyl-O bond fission to form benzyl(trifluoroacetato)palladium complexes 4a-4d. Complexes 4a-4d are in equilibrium in solutions between trans and cis isomers, with the proportion of the cis isomer increasing in polar solvents. Palladium-catalyzed carbonylation of benzyl trifluoroacetate has been achieved in the presence of benzyl alcohol arid triethylamine to yield benzyl phenylacetate.",

author = "Kazuhiro Nagayama and Isao Shimizu and Akio Yamamoto",

year = "1999",

month = apr,

doi = "10.1246/bcsj.72.799",

language = "English",

volume = "72",

pages = "799--803",

journal = "Bulletin of the Chemical Society of Japan",

issn = "0009-2673",

publisher = "Chemical Society of Japan",

number = "4",

}

TY - JOUR

T1 - Oxidative addition of aryl and benzyl trifluoroacetates to zerovalent palladium complexes with two modes of C-O bond cleavage processes

AU - Nagayama, Kazuhiro

AU - Shimizu, Isao

AU - Yamamoto, Akio

PY - 1999/4

Y1 - 1999/4

N2 - The aryl trifluoroacetates oxidatively added to a zerovalent palladium complex 2a with acyl-O bond cleavage under mild conditions to give the corresponding trans-(aryloxo)(trifluoroacetyl)palladium complexes 3a-3c. But 4-nitrophenyl trifluoroacetate reacted with 2a to yield cis-[Pd(OC6H4-4- NO2)2(PMe3)2] 3d, which was produced with C-O bond activation followed by disproportionation reaction. In contrast, benzyl trifluoroacetates reacted with the Pd(0) complex with benzyl-O bond fission to form benzyl(trifluoroacetato)palladium complexes 4a-4d. Complexes 4a-4d are in equilibrium in solutions between trans and cis isomers, with the proportion of the cis isomer increasing in polar solvents. Palladium-catalyzed carbonylation of benzyl trifluoroacetate has been achieved in the presence of benzyl alcohol arid triethylamine to yield benzyl phenylacetate.

AB - The aryl trifluoroacetates oxidatively added to a zerovalent palladium complex 2a with acyl-O bond cleavage under mild conditions to give the corresponding trans-(aryloxo)(trifluoroacetyl)palladium complexes 3a-3c. But 4-nitrophenyl trifluoroacetate reacted with 2a to yield cis-[Pd(OC6H4-4- NO2)2(PMe3)2] 3d, which was produced with C-O bond activation followed by disproportionation reaction. In contrast, benzyl trifluoroacetates reacted with the Pd(0) complex with benzyl-O bond fission to form benzyl(trifluoroacetato)palladium complexes 4a-4d. Complexes 4a-4d are in equilibrium in solutions between trans and cis isomers, with the proportion of the cis isomer increasing in polar solvents. Palladium-catalyzed carbonylation of benzyl trifluoroacetate has been achieved in the presence of benzyl alcohol arid triethylamine to yield benzyl phenylacetate.

UR - http://www.scopus.com/inward/record.url?scp=0032962645&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0032962645&partnerID=8YFLogxK

U2 - 10.1246/bcsj.72.799

DO - 10.1246/bcsj.72.799

M3 - Article

AN - SCOPUS:0032962645

SN - 0009-2673

VL - 72

SP - 799

EP - 803

JO - Bulletin of the Chemical Society of Japan

JF - Bulletin of the Chemical Society of Japan

IS - 4

ER -

Oxidative addition of aryl and benzyl trifluoroacetates to zerovalent palladium complexes with two modes of C-O bond cleavage processes

Abstract

ASJC Scopus subject areas

Access to Document

Other files and links

Fingerprint

Cite this