FranÅois-Xavier Legrand et al.
FULL PAPERS
spectrometer operating at 300.13 MHz for 1H nuclei,
75.47 MHz for 13C nuclei and 121.49 MHz for 31P nuclei. 1D
and 2D NMR experiments were obtained using the pulse
programs available from the Bruker library. Details concern-
ing experimental conditions are given in the Figure captions.
All NMR measurements were performed under careful tem-
perature regulation using a Bruker BVT variable tempera-
ture unit. Chemical shifts are given in parts per million
(ppm) relative to external reference using internal capillary
[sodium salt of 3-(trimethylsilyl)-2,2,3,3-tetradeuteropro-
ionic strength of the medium as the total concentra-
tion of sodium carboxylate groups was kept constant.
Indeed, when the concentration of ACNa increased,
the concentration of III decreased in the same pro-
portion.
Conclusions
1
pionic acid (98% atom D) in D2O for H and 13C NMR and
To summarize, we have successfully prepared a new
CD-phosphane bearing a triphenylphosphane group
and no self-inclusion phenomenon was observed.
TEM studies have shown that PM-b-CD-OTPP aggre-
gated by forming a stable dispersion in water. Its
water-solubility can be dramatically increased in the
presence of water-soluble selected guests by a phe-
nomenon of hydrophilic assistance. PM-b-CD-OTPP
associated to a rhodium precursor is able to generate
soluble rhodium species in water. Interestingly, the
PM-b-CD-OTPP cavity remains available even if this
ligand is coordinated to rhodium. Rhodium-catalyzed
hydrogenation and hydroformylation reactions of
water-soluble substrates can be performed by using
PM-b-CD-OTPP as ligand. Interestingly, the catalytic
activity was dramatically higher when the substrate
can be included into the CD cavity. With a non-inter-
acting substrate, it was also demonstrated that the
presence of a guest inside the cavity did not modify
the catalytic performance. These results open very in-
teresting perspectives to heterogenize homogeneous
catalysts by anchoring PM-b-CD-OTPP on surfaces or
polymeric materials bearing pendant groups. This new
strategy could also create confined media favourable
to specific selectivity.
H3PO4 in H2O for 31P NMR] and calibration was performed
using the signal of the residual signals of the solvent as a
secondary reference while taking into account temperature
effects.
The MALDI-TOF mass spectra were recorded on a
MALDI-TOF-TOF Bruker Daltonics Ultraflex II spectrom-
eter in positive reflectron mode using 2,5-dihydroxybenzoic
acid as matrix and external peptide calibration standard kit
(Bruker Daltonics) within the 750–4200 mass range. The ac-
celeration voltage was fixed at 25 keV, the delayed extrac-
tion time at 10 ns and the number of laser shots at 200. The
samples were dissolved at 10 mM either in water, acetone or
methanol and equally mixed with the matrix solution
[10 mgmLÀ1 of 2,5-DHB in water/0.1% trifloroacetic acid:a-
cetonitrile, 70:30 (v/v)] and spotted onto a ground style
MALDI target according to the dried droplet method.
Gas chromatographic analyses were carried out on a Shi-
madzu GC-17A gas chromatograph equipped with a polydi-
methylsiloxane capillary column (30 mꢂ0.32 mm) and a
flame ionization detector (GC:FID).
Synthesis of 6A-O-[4-(Diphenylphosphino)phenyl]-
2A,2B,2C,2D,2E,2F,2G,3A,3B,3C,3D,3E,3F,3G,6B,6C,6D,6E,6F,6G-
eicosa-O-methyl-b-cyclodextrin
A
solution
of
dried
6A-O-(p-tolylsulfonyl)-
2A,2B,2C,2D,2E,2F,2G,3A,3B,3C,3D,3E,3F,3G,6B,6C,6D,6E,6F,6G-eicosa-
O-methyl-b-cyclodextrin (1.0 g, 0.64 mmol), 4-(diphenyl-
phosphino)phenol (178 mg, 0.64 mmol) and cesium carbon-
ate (209 mg, 0.64 mmol) in dry DMF (10 mL) was stirred for
4 days at 808C under nitrogen. Next, degassed deionized
(10 mL) water was added. The product was extracted under
N2 with degassed ethyl acetate (2ꢂ10 mL). After evapora-
tion of the solvent, the obtained oil was dissolved in chloro-
form (10 mL) and washed under nitrogen with water (20ꢂ
10 mL). After evaporation of chloroform, the 6A-O-[4-(di-
phenylphosphino)phenyl]-2A,2B,2C,2D,2E,2F,2G,3A,3B,3C,3D,3E,
Experimental Section
Materials and Apparatus
The starting b-cyclodextrin was a generous gift of Roquette
Frꢃres
(Lestrem,
France).
6A-O-(p-Tolylsulfonyl)-
2A,2B,2C,2D,2E,2F,2G,3A,3B,3C,3D,3E,3F,3G,6B,6C,6D,6E,6F,6G-eicosa-
O-methyl-b-cyclodextrin was obtained in two steps from the
native b-cyclodextrin, as already described in the litera-
ture.[12,13] The most of chemical products, reagents and sol-
vents used in this study was purchased from Acros Organics
and Sigma–Aldrich in their highest purity and used without
further purification. Catalytic precursors and deuterated sol-
vents were purchased respectively from Strem Chemicals
and Euriso-Top in their highest purity and used without fur-
ther purification. Distilled water was used in all experi-
ments. 4-(Diphenylphosphino)phenol was prepared in three
steps from 4-bromoanisole according to literature meth-
ods.[27] Carbon monoxide/dihydrogen mixture (1:1) and dihy-
drogen were used directly from cylinders (>99.9% pure;
Air Liquide).
3F,3G,6B,6C,6D,6E,6F,6G-eicosa-O-methyl-b-cyclodextrin
was
obtained as a white amorphous solid; yield: 0.95 g (90%).
1H NMR (300.13 MHz, CDCl3, 293.15 K): d=7.40–7.15 (m,
3
12H, Hc, Hb’, Hc’, Hd’), 6.96 (d, 2H, JH ,H =8.1 Hz, Hb),
b
c
5.30–5.00 (m, 7H, H1A–G), 4.42 (d, 1H, JH ,H =10.0 Hz, H6
2
A
6
6’
or H6’A), 4.31 (d, 1H, JH ,H =9.8 Hz, H6 or H6’A), 4.20–2.80
2
A
(m, 100H, H2A–G, H3A–G,6 H4A–G, H5A-G, H6B–G, H6’B–G, MeO-
6’
A–G
A–G
C2
,
MeO-C3
,
MeO-C6B–G); 1H NMR (300.13 MHz,
DMSO-d6, 293.15 K): d=7.35 (m, 6H, Hc’, Hd’), 7.18 (m,
3
6H, Hc, Hb’), 6.96 (d, 2H, JH ,H =8.1 Hz, Hb), 5.16–4.90 (m,
b
c
7H, H1A–G), 4.26 (m, 1H, H6 or H6’A), 3,90 (m, H6 or
A
A
H6’A), 3.80–2.90 (m, 100H, H2A–G, H3A–G, H4A–G, H5A–G, H6
,
B–G
Characterization and structure determinations were ach-
ieved by NMR experiments on a Bruker Avance DRX300
H6’B–G, MeO-C2A–G, MeO-C3A–G, MeO-C6B–G);13C{1H} NMR
(75.47 MHz, CDCl3, 293.15 K): d=159.4 (s, 1C, Ca), 137.7
1332
ꢁ 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Adv. Synth. Catal. 2011, 353, 1325 – 1334