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diluted with ether (10 mL), dodecane (250 mL) was introduced (in-
ternal standard for GC analysis), and the organic layer was extract-
ed and analyzed by GC. ICP analysis was performed on the sample.
Acknowledgements
We are grateful to the Agence nationale de la recherche (ANR)
for financial support dedicated to project ISOSORB-CO (2010-006-
01). Roquette Frres is gratefully acknowledged for providing
pure samples of isosorbide. Isosorbide is part of the BIOHUB pro-
gram (http://www.biohub.fr).
General procedure to isolate the esters (Table 3)
The crude product was extracted with ether (210 mL). The ether
phase was washed with distilled water (10 mL), and the resulting
solution was dried (MgSO4) and filtered. The volatiles were finally
evaporated under reduced pressure to afford the mixture of esters
as a colorless liquid.
Keywords: biphasic catalysis
hydroesterification · palladium · polyols
· homogeneous catalysis ·
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Synthesis of ligand L2
A 250 mL Schlenk tube equipped with a magnetic stirring bar was
charged with 1-(4-bromophenyl)-N,N-dimethylmethanamine (3.3 g,
15.41 mmol). The Schlenk tube was purged with nitrogen by using
vacuum/N2 cycles (3), and degassed diethyl ether (50 mL) was
added to the flask by cannula. The resulting homogeneous solu-
tion was cooled down to À788C. A solution of 1.6m tert-butyllithi-
um in pentane (20 mL, 32 mmol) was then added dropwise while
maintaining the temperature. A yellowish precipitate was formed,
and the solution was stirred at À788C for 2 h under an atmosphere
of nitrogen. Dichlorophenylphosphine (1000 mL, 7.37 mmol) was
added dropwise by syringe, and the solution was kept at room
temperature and stirred overnight. Degassed water (50 mL) was
added, followed by degassed dichloromethane (50 mL). After de-
cantation, the organic layer was extracted, and the aqueous phase
was further extracted with degassed dichloromethane (225 mL).
The organic layer was dried (MgSO4), and after filtration (under an
atmosphere of nitrogen) the volatiles were evaporated. The prod-
uct was finally obtained as a pale-yellow oil (2.16 g, 80%). The
oxide-free ligand was obtained through a reduction step with
HSiCl3 according to a reported procedure.[14] 1H NMR (300 MHz,
CDCl3): d=2.27 (s, 12H, CH3), 3.44 (s, 4H, CH2), 7.31 ppm (m, 13H,
Harom). 13C NMR (75 MHz, CDCl3): d=45.43 (s, 4C, CH3), 64.07 (s, 2C,
CH2), 128.46 (d, JP,C = 6.8 Hz, 2C, CHmeta), 128.62 (s, 1C, CHpara),
129.25 (d, JP,C = 7.1 Hz, 4C, CHmeta), 133.67 (d, JP,C = 19.4 Hz, 2C,
CHortho), 133.73 (d, JP,C = 19.7 Hz, 4C, CHortho), 135.88 (d, JP,C = 10.4 Hz,
2C, Cipso), 137.52 (d, JP,C = 10.9 Hz, 1C, Cipso), 139.54 ppm (s, 1C,
CCH2). 31P NMR (121 MHz, CDCl3): d=À6.7 ppm.
Synthesis of ligand L1
The ligand was synthesized accordingly to the protocol used for
the synthesis of L2. The reaction was set up with 1-(4-bromophen-
yl)-N,N-dimethylmethanamine (1,3 g, 6 mmol), 1.6m tert-butyllithi-
um in pentane (9 mL, 14.4 mmol), and chlorodiphenylphosphine
(1100 mL, 6 mmol). The product was finally obtained as a pale-
yellow oil (1.78 g, 91%). H NMR (300 MHz, CDCl3): d=2.28 (s, 6H,
CH3), 3.45 (s, 2H, CH2), 7.28–7.37 ppm (m, 14H, Harom). 13C NMR
(75 MHz, CDCl3): d=45.42 (s, 4C, CH3), 64.04 (s, 2C, CH2), 128.48 (d,
[12] R. Pruvost, J. Boulanger, B. LØger, A. Ponchel, E. Monflier, M. Ibert, A.
[14] R. Kreiter, J. J. Firet, M. J. J. Ruts, M. Lutz, A. L. Spek, R. J. M. Klein Geb-
1
J
P,C = 7.1 Hz, 4C, CHmeta), 128.67 (s, 2C, CHpara), 129.29 (d, JP,C
=
7,1 Hz, 2C, CHmeta), 133.71 (d, JP,C = 19.4 Hz, 4C, CHortho), 133.77 (d,
J
P,C = 19.6 Hz, 4C, CHortho), 135.92 (d, JP,C = 10.4 Hz, 2C, Cipso), 137.33
Received: December 11, 2014
Revised: March 16, 2015
Published online on June 3, 2015
(d, JP,C = 10.9 Hz, 2C, Cipso), 139.50 (s, 1C, CCH2). 31P NMR (121 MHz,
CDCl3): d=À6.0 ppm.
ChemSusChem 2015, 8, 2133 – 2137
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