Irreversible Catalytic Ester Hydrolysis of Allyl Esters to Give Acids and Aldehydes
bar. To the tube was added dry CH2Cl2 (0.5 mL) and the
mixture was stirred for 20 min at room temperature under a
nitrogen atmosphere. After removal of the solvent, the solid
was dried under vacuum for 1 h. A mixture of 1a (1.0 mmol,
162 mg), solvent (1 mL), water (2.0 mmol, 36 mL) and di-
glyme (0.25 mmol, 35 mL, internal standard for GC analysis)
was placed into a 20-mL Schlenk tube, and the mixture was
degassed by two freeze-thaw cycles. This mixture was trans-
ferred via cannula to the screw cap test-tube which contains
the Ru/Pd catalyst. The mixture was stirred at 858C for
20 min. After cooling to room temperature, the yield of the
product was determined by GC analysis.
the mixture was degassed by two freeze-thaw cycles. This
mixture was transferred via cannula to the screw cap test-
tube which contains the Ru/Pd catalyst. The mixture was
stirred at 858C for 30 min. After cooling to room tempera-
ture, the yield of the product was determined by GC analy-
sis (2h > 99% yield, 3 >99% yield).
Supporting Information
Complete experimental procedures, NMR data (1b, 1c, 1d,
1e, 1f, 1g, 1k, 1l, 1m, 1n, 5 and 6), and Figure S-1–S-7 are
available as Supporting Information.
Hydrolysis of Allyl Benzoate (1a), Table 5, entries 1–
10
Acknowledgements
A
ACHTUNGTRENNUNG
screw cap test-tube was charged with [Ru(Cp)-
(MeCN)3]PF6 (0.010 mmol, 4.3 mg), bidentate phosphine
(0.010 mmol), PdCl2A(MeCN)2 (0.010 mmol, 2.6 mg) and stir-
This study was supported by Industrial Technology Research
Grant Program in 2005 from New Energy and Industrial
Technology Development Organization (NEDO) of Japan.
The present work is also supported by a Grant-in-Aid for
Global-COE program, “Science for Future Molecular Sys-
tems”, Scientific Research (A) (No. 20245014), and on Priori-
ty Areas (No. 20037052, Chemistry of Concerto Catalysis)
from the Ministry of Education, Culture, Science, Sports and
Technology of Japan.
CTHUNGTRENNUNG
ring bar. To the tube was added dry CH2Cl2 (0.5 mL) and
the mixture was stirred for 20 min at room temperature
under a nitrogen atmosphere. After removal of the solvent,
the solid was dried under vacuum for 1 h. A mixture of 1a
(1.0 mmol, 162 mg), DME (1 mL), water (2.0 mmol, 36 mL)
and diglyme (0.25 mmol, 35 mL, internal standard for GC
analysis) was placed into a 20-mL Schlenk tube, and the
mixture was degassed by two freeze-thaw cycles. This mix-
ture was transferred via cannula to the screw cap test-tube
which contains the Ru/Pd catalyst. The mixture was stirred
at 858C for 20 min. After cooling to room temperature, the
yield of the product was determined by GC analysis.
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Hydrolysis of Various Allyl Esters (1a–1n), Table 6,
entries 1–14
A
ACHTUNGTRENNUNG
screw cap test-tube was charged with [Ru(Cp)-
(MeCN)3]PF6 (5.0–10.0 mmol), DPPHex (5.0–10.0 mmol),
PdCl2A(MeCN)2 (5.0–10.0 mmol) and stirring bar. To the tube
CHTUNGTRENNUNG
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for 20 min at room temperature under a nitrogen atmos-
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under vacuum for 1 h. A mixture of 1a–1n (1.0 mmol),
DME (1 mL), water (2.0 mmol, 36 mL) and diglyme
(0.25 mmol, 35 mL, internal standard for GC analysis) was
placed into a 20-mL Schlenk tube, and the mixture was de-
gassed by two freeze-thaw cycles. This mixture was trans-
ferred via cannula to the screw cap test-tube which contains
the Ru/Pd catalyst. The mixture was stirred at 858C for 10–
120 min. After cooling to room temperature, the yield of the
product was determined by GC analysis.
Hydrolysis Reaction, Scheme 4 (10 mmol Scale
Reaction)
A
G
screw cap test-tube was charged with [Ru(Cp)-
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temperature under a nitrogen atmosphere. After removal of
the solvent, the solid was dried under vacuum for 1 h. A
mixture of 1h (10 mmol), DME (10 mL), water (20 mmol,
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for GC analysis) was placed into a 20-mL Schlenk tube, and
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Adv. Synth. Catal. 2011, 353, 973 – 984
ꢁ 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
983