CHIRALITY 12:411420 (2000)

Immobilization of Rhodium Complexes in Chiral

OrganicInorganic Hybrid Materials
AUGUSTIN ADIMA, JOE L J.E. MOREAU,* AND MICHEL WONG CHI MAN
Laboratoire de Chimie Organometallique, Ecole Nationale Superieure de Chimie de Montpellier,
Montpellier, France

ABSTRACT Two new alkoxysilylated derivatives of ()-(1R,2R)-1,2-diaminocyclo-

hexane: M = N-[(triethoxysilyl)propyl]-()-(1R,2R)-1,2-diaminocyclohexane and B =
N,N-bis[(triethoxysilyl)propyl]-()-(1R,2R)-1,2-diaminocyclohexane have been synthe-
sized. Their complexation with [Rh(cod)Cl]2 in the presence of TEOS = Si(OEt)4, fol-
lowed by sol-gel hydrolysis-condensation, afforded new catalytic chiral hybrid materials.
Evidence for the presence of the organic moieties complexed by rhodium in these solids
was obtained by UV-visible spectroscopy, FT-IR studies, solid state 13C and 29Si CP-MAS
NMR analysis, energy-dispersive X-ray (EDX) techniques, and elemental analysis. The
nitrogen sorption studies and BET analyses ranged these solid gels from nonporous to
highly porous materials. The catalytic activities and selectivities of the solid materials
have been studied in the asymmetric hydrogen-transfer reduction of prochiral ketones
and compared to that of the homogeneous rhodium complexes of the ligands M and B.
The hybrid materials appeared interesting supports for enantioselective heterogeneous
catalysis leading to chiral alcohols with ee up to 58% in the reduction of acetophenone
and up to 98% in the case of the more hindered related ketones. The catalytic properties
as a function of the nature of chiral hybrid solid are discussed. Chirality 12:411420,
2000. 2000 Wiley-Liss, Inc.

KEY WORDS: hybrid materials; chiral polymeric networks; sol-gel process; heteroge-
neous catalysts ()-(1R,2R)-1,2-diaminocyclohexane; enantioselective
catalysts; hydrogen-transfer reduction

One of the most important areas of synthetic organic
chemistry consists in developing new methodologies for
efficient asymmetric syntheses. Many organic molecules
can now be synthesized with near-complete enantioselec-
tivity.16 Bidentate auxiliaries with C2 symmetry have at-
tracted much attention and proved to be highly efficient,
leading to high asymmetric induction in chemical transfor-
mations.7 Transition metal complexes containing chelating
ligands with C2 symmetry also constitute the most inter-
esting class of chiral catalysts to achieve homogeneous
asymmetric reactions.4 Complexes of transition metals
containing Noyoris BINAP ligand,811 for example, allow
the asymmetric hydrogenation reaction of unsaturated sub-
strates or the asymmetric isomerization of allylic amines
with extremely high enantioselectivities. Even simple and
readily available molecules such as trans-1,2-diamino-
cyclohexane derivatives were shown to be of great interest
as chiral reagents, as scaffolds, or as ligands for catalysis.12
Most of the above reactions were performed in homoge-
neous media. The problems associated with the recovery
of homogeneous catalysts and their separation from the
reaction products1318 and the difficulties associated with
the recycling of the catalytic species have in part been
addressed by immobilization on a heterogeneous solid sup-
port such as polymers or silicas.1926 The grafting of chiral
ligands on the surface of organic or inorganic polymers
2000 Wiley-Liss, Inc.
opens the possibility to heterogenize transition metal cata-
lytic species. However, problems related to the stability
and selectivity of the catalyst sometimes remain and sup-
ported homogeneous catalysts do not always compare fa-
vorably with the soluble catalytic species.19 The develop-
ment and the design of enantioselective heterogenous cata-
lysts is still a challenging area.27,28
In the last decade the sol-gel process, which emerged as
a very interesting way to prepare inorganic materials29 was
successfully used to prepare heterogeneous catalysts.30,31
Moreover, owing to the mild reaction conditions used, the
sol-gel chemistry allows easy preparation of hybrid solid
materials.32,33 Hybrid silica-based materials, which can be
simply defined as a solid associating an organic component
and a silica fragment, are receiving much attention owing
to their well-defined structure and their stability.3442 The
hydrolysis-condensation reaction of organic molecules
functionalized by Si(OR)3 groups leads to a wide variety of
Dedicated to Professor Ryoji Noyori in recognition of his outstanding in-
novative contributions.
*Correspondence to: Joel J.E. Moreau, Laboratoire de Chimie Organo-
metallique, UMR CNRS 5076, Ecole Nationale Superieure de Chimie de
Montpellier, 8 rue de lEcole Normale, 34296 Montpellier Cedex 05,
France. E-mail: jmoreau@cit.enscm.fr
Received for publication 29 November 1999; Accepted 13 January 2000
412
Scheme 1. Sol-gel hydrolysis of poly(trialkoxy)organosilanes.
hybrid polysilsesquioxane gels. The presence of nonhydro-
lysable Si-C bonds35,36 led to a 3D network which can be
described as siloxane chains cross-linked by bridging or-
ganic substructures (Scheme 1). This approach offers
great potential for material design in many applications.
Highly porous materials with high surface areas have been
obtained in some cases, attributed to the rigid property of
the cross-linking organic moieties.35,36 A control of the
pore structure has also been reported by the use of a mo-
lecular template.4145
The sol-gel processing of organofunctional metal alkox-
ides has also been used to prepare hybrids containing tran-
sition metal. The incorporation of Lewis bases or ligands
has led to materials with complexing or catalytic proper-
ties.46,47 Heterogeneous metal catalysts and immobilized
molecular catalytic species with high stability have been
reported using a sol-gel approach.46,47 Very recently, new
hybrid silica gels with bidentate malonamide units have
been shown to be highly efficient extracting solids for ac-
tinides.48 The approach involving hybrid organic-inorganic
materials is quite interesting since the properties of the
material can be tailored on a molecular basis according to
the structure and properties of the precursors (Scheme 1).
Our current interest in the use of hybrid silicas as sup-
port for heterogeneous catalysts49,50 has led us to investi-
gate the incorporation of chiral organic molecules in the
mixed 3D network of hybrids. We were particularly inter-
ested in incorporating molecules with C2 symmetry, to pro-
duce a chiral polymeric hybrid network, and in immobiliz-
ing transition metal complexes on these chiral supports.
We report here the preparation of hybrid solids containing
(1R,2R)-diaminocyclohexane units and their use to immo-
bilize rhodium catalysts. We explored the preparation of
various gels containing rhodium chiral diamine complexes.
The catalyst selectivity has been studied as a function of
the structure and stoichiometry of the hybrid using mono-
silylated or bis-silylated chiral diamine precursors. Part of
this work has been previously published.51
RESULTS AND DISCUSSION
Synthesis of the Functionalized Diamines M and B
The synthesis of monosilylated M and bis-silylated B
amines (Scheme 2) was performed with ()-(1R,2R)-
diaminocyclohexane after resolution of commercially avail-
ADIMA ET AL.
Scheme 2. Synthesis of molecular precursors M and B.
able mixture of cis and trans-diaminocyclohexane (30/70)
according to the literature.52,53
The preparations of the monosilylated M and the bis-
silylated derivatives B, were achieved stepwise to avoid the
formation of a mixture of both M and B, which were found
difficult to separate. A mixture containing a 2:1 molar ratio
of ()-(1R,2R)-1,2-diaminocyclohexane and (3-chloro-
propyl)triethoxysilane was heated to 87C in a sealed tube
for 18 h. The extraction with pentane followed by filtration
and then distillation at reduced pressure afforded M as a
colorless liquid in 70% yield. B was obtained in a 60% yield
as a crude viscous liquid, following a similar procedure
with a 2:1 molar mixture of M and (3-chloropropyl)trieth-
oxysilane at 110C for 18 h.
Synthesis and Characterization of the Chiral
Hybrid Materials
The hydrolysis-condensation of the precursors M and B
were performed with or without added tetraethoxysilane
(TEOS) under mild reaction conditions in ethanol by add-
ing a stoichiometric amount of water. For characterization
studies and for comparison we first prepared hybrid gels
(without incorporating rhodium) from M and B. No gel
formation occurred upon hydrolysis of pure M. It was ob-
tained upon co-hydrolysis condensation with added TEOS.
The hydrolysis of pure B containing two silyl substituents
rapidly gave a gel. In all cases gelation occurred within 3 h
without the use of any added catalyst. Nucleophilic activa-
tion by the nitrogen atoms present in M and B accounts for
the fast hydrolysis-condensation process.54,55 After the for-
mation of the gels, these were aged for 1 week, then pow-
dered, washed, and dried under vacuum and analyzed.
The synthesis of the gel from monosilylated compound
M was achieved in the presence of 5 mol equivalent of
TEOS (Scheme 3). The gel, M-5, (M stands for monosi-
lylated derivative and 5 for the number of moles of TEOS)
was obtained quantitatively.
The synthesis of the gels from the bis-silylated com-
pound B was obtained without addition of TEOS owing to
the two functional trialkoxysilyl groups which allow an
easy cross-linking of the silicate framework.35,36 Addition
of 2 mol equivalent of H2O to a solution of B in EtOH
rapidly led to gel B-0 (B stands for bis-silylated and 0 for
the absence of TEOS) (Scheme 4).
The solid stoichiometry was determined upon elemental
 IMMOBILIZATION OF RHODIUM COMPLEXES 413

Scheme 3. Synthesis of monosilylated gel M-5.

analysis of the obtained material. It differs somewhat from

the silsesquioxane stoichiometry shown in Schemes 3 and
4, used there for simplicity. It indicates that the material
contained remaining uncondensed OH and OEt groups at
silicon. The results are quite similar to those of previous
observations with related materials.36,37
The hybrid gel containing the chiral diaminocyclohex-
ane units were characterized by IR and solid state 13C and
29
Si NMR. The measurements were performed using the
CP-MAS technique in order to enhance signal intensity.56 Scheme 4. Synthesis of bis-silylated gel B-0.
The 13C solid state NMR are consistent with the presence
of the organic unit in the hybrid network (cf. Fig. 1). The
gel M-5 exhibits two very broad signals at 5075 and 2050
ppm. The first one corresponds to the carbon atoms linked
to nitrogen and to residual uncondensed ethoxy groups
(O-CH2). The second one corresponds to the cyclic and
also inner carbon atom of the n-propyl group (C-CH2-C).
Two signals centered at 18 and 8 ppm are also present in
the spectrum corresponding, respectively, to the methyl
carbon of residual ethoxy group and to the carbon atom
bonded to silicon. The spectrum of gel B-0 is similar, with
two broad signals at 2040 ppm and 5068 ppm, a sharp
signal at 18 ppm (residual ethoxy group), and a weak signal
at 8 ppm.
The 29Si solid state NMR allowed the characterization of
the silicate substructures in the hybrid network. Again, the
CP-MAS technique was used so as to recover higher signal
intensity for these materials. The gel M-5 presented a
spectrum with essentially two groups of signals (Fig. 2).
The first is a broad signal centered at -66 ppm correspond-
ing to T units (trifunctional silicate: C-SiO3) and the second
at -103 and -110 ppm represents the different Q units
13
(quadrifunctional silicate: SiO4). The gel prepared without FIG. 1. C CP-MAS solid state NMR of B-5.
TEOS, B-0, exhibits only a large peak from 50 to 75 ppm
(Fig. 2). It represents overlapping signals corresponding to
T units (C-SiO3). The absence of signal in the region 100,
110 ppm demonstrates that no cleavage of the Si-C bonds
had occurred during gel formation.
The surface properties of gels M-5 and B-0 were stud-
ied by nitrogen sorption experiments according to BET.57
Surface areas of 280 m2 g1 and 20 m2 g1 were respectively
determined for materials M-5 and B-0.

Rhodium Complexes Containing Chiral

Hybrid Materials
We then studied the incorporation of rhodium species in
the hybrid network. The approach was first to form a rho-
dium complex with the diamine precursor and then to per-
form hydrolysis to prepare the hybrid gel. In this way the FIG. 2. 29
Si CP-MAS solid state NMR of M-5 and B-0.
414 ADIMA ET AL.

Scheme 5. Synthesis of rhodium-complexed monosilylated gels with TEOS.

solid material is built around the metal species. It differs the solid material appeared similar to the species in solu-
from the classical grafting of a metallic species at the sur- tion.
face of a solid material and may give the complex a higher The rhodium-containing hybrids were also studied by
stability. It may result in enhanced stability of the catalytic solid-state NMR. The CP-MAS 13C NMR spectra of gels
materials. MRh-2 and MRh-5 are similar to that of the correspond-
ing noncomplexed gel M-5, apart from a broad signal rang-
Synthesis of gels from monosilylated precursor M. ing from 7090 ppm. This broad signal corresponds to the
The precursor M was first reacted with 0.5 mol equiva- sp2 carbon of cyclooctadiene (cod) ligand initially com-
lent of [Rh(cod)Cl]2 in ethanol. Evidence for the complex- plexed with [Rh(cod)Cl]2. It appears that the cod ligand is
ation of the diamine ligand M with [Rh(cod)Cl]2 in ethanol retained in the coordination sphere of the rhodium atom in
as solvent was obtained by UV-visible analysis. The rho- the solid material. The 29Si CP-MAS NMR spectra of
dium dimer [Rh(cod)Cl]2 complex exhibits an absorption MRh-2 and MRh-5 are similar to that of the rhodium free
at 350 nm. Upon reaction with M, a new absorption maxima hybrid M-5.
appears at 383 nm. The intermediate complex of M was The BET surface areas of the two materials were deter-
then subjected to hydrolysis and condensation in the pres- mined and the results are shown in Table 1. A low surface
ence of added TEOS (Scheme 5). area was found for MRh-2, whereas a much higher value
In order to study the dilution effect of the diamine- was determined in the case of MRh-5. The latter is similar
rhodium complex with TEOS, two gels were prepared from to that of the rhodium-free hybrid M-5.
M with a 2:1 and a 5:1 molar ratio of TEOS: M respectively For comparison, another catalytic material, MRh-GS,
called gels MRh-2 and MRh-5, (Rh stands for rhodium- (GS means grafted silica) was prepared using a conven-
complexed material). tional immobilization technique. After activation of a com-
The compositions of all these materials were analyzed by mercial high surface area silica58,59 the ligand M was
atomic percent determination using EDX techniques and grafted following the literature method.60 The immobilized
also by elemental analysis. The results are summarized in ligand was then complexed with [Rh(cod)Cl]2 to give
Table 1, and shows a quantitative incorporation of rhodium MRh-GS (Scheme 6).
into the hybrid material. Solid UV-visible analyses per-
formed on the gels also showed the presence of an absorp- Synthesis of gels from bis-silylated precursor B. The
tion maximum at 383 nm. The rhodium diamine complex in rhodium-containing hybrids were prepared from B in a
way similar to that used in the case of M. The bis-silylated
precursor B was first treated with [Rh(cod)Cl]2 in EtOH to
TABLE 1. EDX, elementary, and surface area analysis of give a species which exhibits a UV-visible absorption
rhodium-complexed gels maxima at 383 nm. It was then hydrolyzed with or without
added TEOS (Scheme 7).
EDX Elem.
Theoretical analysis Anal. Surface area
Gel Rh/Si Rh/Si Rh/Si m2 g1
MRh-2 0.33 0.33 0.32 3
MRh-5 0.16 0.16 0.16 224
MRh-GS 0.09 0.09 (a) (a)
BRh-0 0.5 0.49 0.49 5
B1/2Rh-0 0.25 0.25 0.25 (a)
BRh-1 0.33 (a) 0.33 3
BRh-0 0.2 0.19 (a) 11

(a) Not determined. Scheme 6. Preparation of grafted rhodium-complexed gel, MRh-GS.

 IMMOBILIZATION OF RHODIUM COMPLEXES 415

Scheme 7. Synthesis of rhodium-complexed bis-silylated gels.

Four complexed gels were synthesized according to two Catalytic Properties of the Chiral Hybrids
criteria. Gels BRh-0 and B1/2Rh-0 were prepared with-
out added TEOS, respectively using 1 and 0.5 mol equiva- Chiral diamine transition metal complexes have been
lent [Rh(cod)Cl]2 vs. B in order to study the effect of the used as catalysts for the enantioselective reduction of ke-
amount of the Rh entity in the material. On the other hand, tones.6169 We evaluated our hybrid materials, containing
gels BRh-1 and BRh-3 were synthesized with an identical rhodium chiral diaminocyclohexane complexes, as cata-
1:1 ratio of [Rh(cod)Cl]2 vs. B in the presence of varying lysts in the heterogeneous catalytic transfer hydrogenation
TEOS, 1 mole or 3 moles of TEOS, respectively, in order to reaction.
examine the dilution effect in silica. We first tested the catalytic activities and selectivities of
The solid materials were isolated quantitatively. The ana- the rhodium-complexed molecular precursors, M:Rh and
lytical results (Table 1), as indicated by the Rh to Si ratios, B:Rh, in solution for the hydrogen-transfer reduction of
are consistent with a complete incorporation of Rh in the acetophenone (Scheme 8). The corresponding solid mate-
collected solid material. The UV-visible spectra of BRh-0, rials with various compositions according to their prepara-
B1/2Rh-0, BRh-1, and BRh-3 also showed absorption tion procedure were then tested as enantioselective cata-
maxima at 383 nm similar to the species in solution. The lysts.
solid state NMR analysis showed characteristics similar to The results obtained for the catalysts derived from the
those observed with B-0 and the previous rhodium- monosilylated precursors catalysts are given in Table 2.
containing materials MRh-2 and MRh-5. A broad signal at The solid catalysts MRh-2 and MRh-5 (entries 2, 3) lead
7090 ppm was found in the 13C CP-MAS NMR spectrum of to ee 2225%, significantly higher than that found in the
the gels. This result indicates that the cyclooctadiene moi- case of the homogeneous catalyst M:Rh (entry 1, ee =
ety still remains in the coordination sphere of rhodium in 14%). The stoichiometry of the solid support, which varied
the solid materials. As expected, the 29Si CP-MAS NMR according to the proportion of TEOS added in the prepa-
spectra of BRh-0 and B1/2Rh-0 were not significantly ration of the catalyst (entries 2 and 3), shows no significant
different from the spectrum of B-0. The spectra of BRh-1
and BRh-3 showed additional resonances in the -100 to TABLE 2. Hydrogen-transfer reduction of acetophenone at
-110 ppm region characteristic of the presence of Q (SiO4) room temperature with rhodium complexed M and B and
substructures (resulting from the hydrolysis condensation their corresponding gels
of TEOS) in the hybrid network of these gels. All the hy-
brid gels prepared from bis-silylated precursor B showed Reaction time Conversion
low BET surface areas ranging from 3 to 11 m2 g1 (cf. Entry Catalyst (d) (%) ee (%)
Table 1). 1 M:Rh 5 95 14
2 MRh-2 7 70 22
3 MRh-5 5 80 25
4 MRh-GS 14 10 22
5 B:Rh 5 95 26
6 BRh-0 5 75 58
7 B1/2Rh-0 8 60 54
8 BRh-1 7 60 10
Scheme 8. Hydrogen-transfer reduction of acetophenone with rho- 9 BRh-3 8 20 15
dium-complexed M and B and hybrid gels.
416 ADIMA ET AL.

effect on the enantioselectivity of the reaction since similar TABLE 3. Hydrogen-transfer reduction of prochiral
ees were obtained. ketones with hybrid gel BRh-0 at room temperature
It is interesting to note that the catalyst prepared by
Reaction
using the conventional grafting of the catalytic species at time Conver- ee Config-
the surface of silica gave a similar enantioselectivity (entry Entry R1 R2 (d) sion (%) uration
4). However, larger differences appeared in the catalyst
1 CH3 Ph 5 75 58 S
activity. The highest conversion is obtained for the catalyst
2 C8H17 Ph 7 80 40 S
in solution and the lowest for the grafted species. Interest- 3* CBu Ph 2 100 63 R
ingly the hybrid catalyst showed an efficiency much higher 4 Me o-MePh 7 41 78 S
than the grafted one, although lower than the rhodium 5 Me o-OMePh 7 30 80 S
complex in solution. The higher conversion observed (en- 6 Me m-OMePh 7 72 22 S
tries 2, 3) may be related to a higher stability of the hybrid 7 Me p-OMePh 7 34 39 S
catalyst compared to the rhodium complex immobilized at 8 Me 1Np 7 28 87 S
9 Me 2Np 7 30 98 S
the surface of silica. The catalytic material MRh-5 (entry
3) with higher porosity and surface area than MRh-2 (en- *The reaction was performed at 60C.
try 2) gave a higher conversion. The results obtained with
the catalysts derived from the bis-silylated derivatives are
CONCLUSION
also presented in Table 2.
The major result to be pointed out here is that a better We synthesized hybrid organic-inorganic materials con-
selectivity is found when the gels are prepared without taining chiral units using the sol-gel hydrolysis condensa-
added TEOS (entries 6, 7). The ee obtained in homoge- tion of silylated chiral ()-(1R;2R)-trans-1,2-diamino-
neous conditions (entry 5) is lower than those found with cyclohexane derivatives. The resulting chiral solids are of
the former materials (almost doubled ee). Similar enanti- interest for the preparation of enantioselective heteroge-
oselectivities were obtained (54 and 58%) when the amount neous catalysts. Higher selectivities were obtained from
of rhodium varied in the materials (entries 6, 7). The en- the rhodium-complexed hybrid gels for the hydrogen-
transfer reduction of acetophenone compared to those per-
antioselectivity results are better than those found for ma-
formed in homogeneous media. The gels prepared from
terials prepared from the monosilylated derivative. Entries
pure bis-silylated ligand rhodium complex gave the highest
8 and 9 show the results obtained with materials prepared
enantioselectivities. An influence of the secondary struc-
with TEOS. When compared with entry 6, for which the ture of the chiral 3D network may account for that en-
material was prepared without TEOS, a marked decrease hanced selectivity. The latter dramatically decreased when
in selectivity occurred. This result may be indicative of the the catalysts were prepared with added TEOS. In this case,
role played by the hybrid silica matrix. When no TEOS was the chiral diaminocyclohexane units are separated owing
used, the network consists of only chiral diaminocyclohex- to the dilution effect in TEOS.
ane units linked by siloxane bridges. The secondary struc-
ture of the chiral 3D network may have some influence on EXPERIMENTAL SECTION
selectivity. When TEOS is added to the preparation, the
All manipulations were performed under inert gas atmo-
diaminocyclohexane units are separated from each other
sphere (N2 or Ar) using a vacuum line and Schlenk tech-
and the selectivities are closer to the other values. The
niques. All solvents were dried and distilled before use
effect of the structure of the hybrid network seems impor- according to standard methods. 1,2-Diaminocyclohexane
tant. It is modified by the addition of TEOS in the prepa- (mixture of cis and trans isomers), (3-chloropropyl)trieth-
ration step but does appear to vary according to the pro- oxysilane and the ketones: acetophenone, 2-methoxyaceto-
portion of rhodium complex. phenone, 3-methoxyacetophenone, and 4-methoxyaceto-
BRh-0 proved to be the catalyst leading to the high- phenone were purchased from Aldrich (Milwaukee, WI).
est selectivities among all those studied. We thus studied n-Nonaphenone, isobutyrophenone, 2-methylacetophe-
the case of the reduction of various prochiral ketones none, and methyl-2-naphthylketone were purchased from
(Scheme 9). Acros and methyl-1-naphthylketone from Fluka (Milwau-
Selectivities ranging from 4098% were observed in the kee, WI). Silica Gel 60 (Lichroprep RP-2) with a specific
hydrogen-transfer reaction, depending on the nature of the surface area of 500 m2g1 was purchased from Merck
aromatic and the alkyl substituents (Table 3). Hindered (Darmstadt, Germany).
ketones lead to enantioselectivities as high as 98%; how- 1
H, 13C and 29Si NMR spectra in solution were recorded
ever the reduction is slow and a low conversion was ob- on Bruker AC-200 and AC-250 spectrometers at room tem-
served. perature using deuterated chloroform as solvent, TMS as
internal reference 13C, and 29Si solid state NMR spectra
were obtained from Bruker FT-AM 200 or FT-AM 400 spec-
trometers using cross-polarization and magic angle spin-
ning techniques (CP-MAS) and TMS as reference for the
chemical shifts. Chemical shifts are given in ppm. Mass
Scheme 9. Hydrogen-transfer reduction of prochiral ketones with BRh-0. spectra were measured on a JEOL MS-DX 300 mass spec-
 IMMOBILIZATION OF RHODIUM COMPLEXES
trometer. Optical rotations were obtained using a Perkin-
Elmer (Norwalk, CT) polarimeter 241. Enantiomeric ex-
cesses (ee) were determined by HPLC analysis using a
chiral cellulose stationary phase (Chiralcel OD column)
with hexane/2-propanol (9:1) as mobile phase (flow of 1
ml/min1) and a UV detector at 250 nm. A Cary 1E appa-
ratus was used for recording the UV-visible electronic ab-
sorption spectra of the metallic complexes in solution. A
Perkin-Elmer Lambda 14 equipped with an integrated
sphere was used for the UV-visible spectra of the solid
materials, with barium sulfate as reference.
Nitrogen surface area measurements were performed
according to the BET method, at 77 K with a Micromeritics
Gemini 2375 equipment. Elemental analyses of the molecu-
lar precursors and the solid materials were carried out by
the Service Central dAnalyse du CNRS at Vernaison,
France. EDX (energy dispersive X-ray) measurements
were also performed to determine the rhodium/chlorine/
silicon atomic percent using a Cambridge instrument-
stereoscan-360 scanning electronic microscope (SEM)
equipped with an EDS-Link AN 10000 probe.
The resolution of trans-1,2-diaminocyclohexane was car-
ried out as described in the literature.53
Synthesis of N-[(triethoxysilyl)propyl]-()-(1R,2R)-
1,2-diaminocyclohexane, M
In a glass tube were introduced 10.5 g (92 mmol) of
()-(1R,2R)-diaminocyclohexane and 11 g (46 mmole) of
(3-chloropropyl)triethoxysilane. The tube was sealed and
placed in an oil bath at 87C. A white precipitate formed
after 0.5 h. The reaction mixture was left at that tempera-
ture overnight (18 h). The sealed tube was opened and the
white solid was rinsed with freshly distilled pentane (3 25
ml). The solvent was pumped off from the filtrate and the
remaining yellowish solution was distilled, yielding a col-
orless liquid corresponding to M (70%). B.P. (0.02 mm Hg)
= 105C. []D20 = 50.6 (c 1.4 ; THF). 1H NMR (CDCl3)
0.6-0.7 (m , 2H); 1.2 (t, 9H); 1.3-2 (m , 10H); 2.1-2.5 (m ,
3H); 2.6-2.7 (m , 1H); 13C NMR 63.9, 58, 55, 50, 36.1, 31.5,
25.3, 23.8, 18.2, 8; 29Si NMR -44.8. Mass spectrum (FAB+;
NBA): 319 [M+H]+. Anal. Calcd. for C15H34N2O3Si: C,
56.56; H, 10.76 ; N,8.79. Found: C, 55.98; H, 10.68; N, 8.56.
Synthesis of
N,N-bis[(triethoxysilyl)propyl]-()-(1R,2R)-
1,2-diaminocyclohexane, B
In a glass tube were introduced 3 g (9.4 mmol) of M and
1.13 g (4.7 mmol) of (3-chloropropyl)triethoxysilane. The
tube was sealed at 110C. After 18 h, the tube was cooled
to room temperature and opened. The pale brown residue
was extracted with freshly distilled pentane (3 25 ml) and
the solution was filtered. The solvent was eliminated in
vacuo leaving a brown viscous liquid corresponding to B.
Attempts to purify B either by distillation or by chroma-
tography failed and led to the decomposition of the prod-
uct. Yield = 60%. []D20 = 46.6 (c 1.2; THF); 1H NMR
(CDCl3) 0.6-0.7 (m, 4H); 1.2 (t, 18H); 1.4 -1.7 (m, 12H);
2-2.1 (m, 4H); 2.6 (m, 2H). 13C NMR 61.3 , 58, 49.7, 31.5,
24.9, 23.5, 18, 7.8; 29Si NMR 44.9. Mass Spectrum (FAB
417
+, NBA) 523 [M+H]+. Anal. Calcd. for C24H54N2O6Si2: C,
55.14; H, 10.41; 5.35. Found = C, 54.56; H, 10.30; N, 5.30.
Preparation of Solid Gel M-5
In a Schlenk tube were successively added 0.9 g of M
(2.8 mmol), 2.9 g of Si (OEt)4 (14 mmol), and 17 ml of dry
ethanol. The solution was stirred at room temperature and
600 l of water (32.2 mmol) were added. An opaque gel
formed after 20 min. This gel was aged for 1 week and was
then ground in a mortar. The white powder was washed
with ether, filtered, and dried under vacuum for 24 h at
60C. 1.5 g of xerogel M-5 were obtained.
FT-IR (KBr, cm1): Si-O = 1061; C-H = 2865, Si-OH
=3409. 13C CP-MAS NMR: 8 (CH2-Si), 18 (CH3) 20-40
(CH2, (cyc), Si-CH2- CH2), 50-68 (O- CH2, N- CH2, N- CH). 29Si
CP-MAS NMR: -68 (T3), -102 (Q3), -109 (Q4). Anal.
Found: C, 23.77; H, 4.90; N, 4.51; Si, 29.5 corresponding to
C11.3H27.8N1.9O13.3Si6. Surface area (BET) = 280 m2 g1.
Preparation of Complexed Solid Gel MRh-2
In a Schlenk tube were successively introduced 0.5 g of
M (1.57 mmol), 0.38 g of [Rh(cod)Cl]2 (0.785 mmol) and 5
ml dry ethanol. The yellow solution was stirred for 20 min
at room temperature and 0.75 g of Si (OEt)4 (3.14 mmol)
followed by 150 l of water (8.63 mmol) were added. A
yellow transparent gel was obtained after 20 min and was
left for 1 week aging. The gel was powdered and constantly
washed with THF for 20 h by means of a soxhlet apparatus.
The mixture was filtered at room temperature for 24 h
yielding 0.6 g of MRh-2. FT-IR (KBr, cm1): Si-O = 1075;
C-H = 2866, 2940; Si-OH = 3406. Anal. by E.D.X (Atomic%):
Si, 59.7; Rh, 20.5 and Cl, 19.8. Surface area (BET) = 3
m2g1.
Preparation of Complexed Solid Gel MRh-5
The same procedure as above was used with: 0.83 g (2.6
mmol) of M; 0.64 g (1.3 mmol) of [Rh(cod)Cl]2; 2.7 g (13
mmol) of Si(OEt)4, 538 l (29.9 mmol) of H2O; 15.6 ml of
dry EtOH. The yellow gel formed after 10 min and after the
usual work-up 1.8 g yellow powder of MRh-5 was obtained.
FT-IR same as above. 13C CP-MAS NMR: 8.1 (CH2-Si); 18
(CH3); 20-40 (CH2 (cyc), Si-CH2-CH2, CH2-CH=CH); 50-68
(CH2-O, N- CH2, N- CH); 70-90 (CH= CH). 29Si CP-MAS
NMR: ppm -66 (T3), -103 (Q3), 110 (Q4). Anal. Found: C,
24.24; H, 4.4; N, 3.02; Si, 21.8; Cl, 3.6; Rh, 10.8 correspond-
ing to C15.6 H33.7 N1.7O15.7Si6Rh0.8Cl0.8. Elemental analysis
by E.D.X. (Atomic%): Si, 75.58; Rh 12.25; Cl, 12.17. Surface
area (BET): 224 m2 g1.
Preparation of Complexed Solid Gel MRh-GS
This material was prepared in three steps from commer-
cial silica.
Step 1: activation of silica. Four g of silica were intro-
duced in a round-bottom flask equipped with a reflux con-
densor; 20 ml of concentrated HCl (36%) was added and
the mixture was refluxed for 4 h. The solution was filtered
and the white powder was washed with distilled water until
neutral pH was attained. The solid was again washed with
acetone (3 times) and dried under vacuum at 180C for
24 h.
418 ADIMA ET AL.
Step 2: grafting of M on the activated silica. In a 50 ml
round-bottom flask were introduced successively 20 ml of
anhydrous toluene, 3 g of activated silica and 2 g (6.3
mmol) of M. The solution was refluxed for 1 day. The
solution was filtered and the solid was washed with acetone
and dried under reduced pressure at 60C. 4.48 g of the
material were obtained. FT-IR (KBr, cm1): Si-O = 1178;
C-H = 2872; Si-OH = 3409. 29Si CP-MAS NMR ppm -66
(T3); -103 (Q3); -111 (Q4). Anal. Found: C, 9.60; H, 1.95; N,
1.85; Si, 37.35 corresponding to C6.6H16N1.1O25.5Si11.
Step 3: complexation with [Rh(cod)Cl]2. In a small
Schlenk tube 1 g (0.6 meq NH/g) of the above functional-
ized silica was mixed with 0.14 g (0.3 mmol) of [Rh-
(cod)Cl]2 in 2 ml of dry ethanol. The mixture was stirred
for 1 day under nitrogen atmosphere at room temperature.
The solution was filtered and the solid was dried under
reduced pressure at room temperature for 16 h, leading to
a yellow powder (1.1 g). FT-IR (KBr, cm1): Si-O = 1096;
C-H = 2865; Si-OH =3463. 29Si CP-MAS NMR: -66 (T3);
-103 (Q3); -111 (Q4). Anal. by E.D.X. (Atomic%): Si, 83.7;
Rh, 8.7; Cl, 7.6.
Preparation of Solid Gel B-0
In a Schlenk tube 0.64 g (1.2 mmol) of B was solubilized
with 1.2 ml of dry ethanol at room temperature. 660 l (3.66
mmol) of water was added. A transparent gel formed within
10 min and was aged for 1 week. The gel was powdered,
washed with ether, filtered, and dried under reduced pres-
sure at 60C for 16 h. A white powder (0.2 g) was obtained.
FT-IR (KBr, cm1): Si-O = 1061; C-H = 2871, 2943; Si-OH ml of degassed 2-propanol was introduced in a two-necked
=3414.13C CP-MAS NMR: 8.1 (CH2-Si); 17.2 (CH3); 20-40
(CH2 cyc, Si CH2- CH2); 58 (CH2-O); 50-58 (CH-N). 29Si
CP-MAS NMR: ppm broad signal -50 to -75 (T2 and T3).
Anal. Found: C, 48.54; H, 8.34; N, 9.04; Si, 18.30 corre-
sponding to C12.24 H25.4 N1.98 O3.03 Si2. Surface area (BET)
= 20 m2 g1.
Preparation of Complexed Solid Gel BRh-0
In a Schlenk tube 0.43 g (0.82 mmol) of B was stirred
with 0.2 g (0.41 mmol) of [Rh (cod)Cl]2 in 0.8 ml of dry
ethanol at room temperature for 20 min. Fifty l (2.46
mmol) of water was then added. A yellow transparent gel
formed after 1 h and after 1 week aging the gel was ground
and washed with THF by means of a soxhlet apparatus for
20 h. After filtration and drying under reduced pressure at
room temperature, a yellow powder (0.5 g) was obtained.
FT-IR (KBr, cm1): Si-O = 1126; CH = 2860, 2931; Si-OH none, and B (60 mg, 0.01 mmol). 95% conversion was ob-
= 3409. 13C CP-MAS NMR: 8.1 (CH2-Si); 17.2 (CH3); 20-40
(CH2 cyc, Si CH2-CH2, CH2H=CH); 50-68 (CH2-O, N- CH2,
N-CH); 70-90 (CH=CH). 29Si CP-MAS NMR: broad signal
50 to 75 (T2 and T3). Anal. Found: C, 41.19; H, 6.89; N,
4.47; Si, 9.75; Cl, 6.66; Rh, 16.05 corresponding
to C19.8H39.4N1.8O5.4Si2Rh0.9Cl1.1. Surface area (BET) = 5
m2 g1.
Preparation of Complexed Solid Gel B1/2Rh-0
The same procedure as above was performed with: 0.6 g
(1.14 mmol) of B; 0.1 g (0.285 mmol) of [Rh(cod)Cl]2; 62 l
(3.42 mmol) of water; 1.14 ml of dry ethanol. A yellow
powder (0.63 g) was obtained. FT-IR, 13C and 29Si CP-MAS
NMR similar as above. Anal. by E.D.X (Atomic%): Si, 66.8;
Rh, 16.8; Cl, 16.4. Surface area (BET) = 6 m2 g1.
Preparation of Complexed Solid Gel BRh-1
The same procedure as for gel BRh-0 was used except
that 1 molar equivalent of Si(OEt)4 to bifunctional diamine
derivative, B, was added to the mixture before hydrolysis.
0.5 g (0.95 mmol) of B; 0.23 g (0.475 mmol) of [Rh-
(cod)Cl]2; 0.2g (0.95 mmol) of Si(OEt)4; 86 l (4.75 mmol)
of water; 3 ml of dry ethanol. A yellow transparent gel
formed after 2.5 h and after work-up 0.47 g of a yellow
powder was obtained. The FT-IR and 13C CP-MAS NMR
are similar to those of gel BRh-0. 29C CP-MAS NMR: 65
(T3); 102 (Q2); 109 (Q4). Anal. by EDX (Atomic%): Si,
59.6; Rh, 20.5; Cl, 19.8. Surface area (BET): 3 m2 g1.
Preparation of Complexed Solid Gel BRh-3
The same procedure as above was used with: 0.37 g (0.7
mmol) of B; 0.173 g (0.35 mmol) of [Rh(cod)Cl]2; 0.4 g (2.1
mmol) of Si(OEt)4; 100 l (6.3 mmol) of water; 3.5 ml of dry
ethanol. A pale yellow gel formed after 20 min leading to a
yellow powder (0.34 g) after the usual work-up. The FT-IR,
CP-MAS (13C and 29Si) spectra are similar to those of gel
BRh-1. Anal. by EDX (Atomic%): Si, 75.0; Rh, 14.6; Cl, 14.4.
Surface area (BET): 11 m2 g1.
Hydrogen-Transfer Reduction of Acetophenone with M
A solution of M (36.8 mg, 0.01 mmol), [Rh(cod)Cl]2
(27.7 mg, 0.056 mmol) and KOH (10 mg, 0.17 mmol) in 20
flask equipped with a magnetic stirrer. The mixture was
stirred for 0.5 h under nitrogen atmosphere at room tem-
perature to allow the formation of the rhodium/diamine
catalyst. The formation of the latter was confirmed by UV-
visible analysis. Acetophenone (1.35, 11.3 mmol) was then
added and the reaction was monitored by capillary gas
chromatography and the ee measured by HPLC using a
Daicel chiracel OD column. After 5 d 95% conversion was
obtained. The reaction mixture was filtered and the solvent
was evaporated. The residue was subjected to column
chromatography on silica gel (eluent: toluene/acetone 9:1)
to give pure 1-phenylethanol. (ee = 14%, yield = 88%).
Hydrogen-Transfer Reduction of Acetophenone with B
The same procedure as above was performed with the
same amount of [Rh(cod)Cl]2 KOH, 2-propanol, acetophe-
tained after 5 d. The same work-up gave pure 1-phenyletha-
nol (ee = 25%, yield = 80%).
General Procedure for the Hydrogen-Transfer
Reduction of Acetophenone with the Solid Materials
In a two-necked flask, solid gel BRh-0 (5.34 mg, 0.083
mmol) corresponding to 1.64 103 equivalent of rhodium
per gram of solid, KOH (14 mg, 0.25 mmol) and 20 ml of
2-propanol were stirred for 0.5 h under nitrogen atmo-
sphere at room temperature. Acetophenone (1 g, 8.3
mmol) was added and the reaction was monitored by cap-
illary gas chromatography. After 5 d (75% conversion) the
solution was filtered and purification by column chroma-
 IMMOBILIZATION OF RHODIUM COMPLEXES
tography on silica gel as previously described afforded
pure 1-phenylethanol (ee = 58%, yield = 60%).
LITERATURE CITED
1. Morrison JD. Asymmetric synthesis. New York: Academic Press; 1985.
2. Bosnich B. Asymmetric catalysis. Dordrecht: Martinus Nijhoff; 1986.
3. Ojima I. Catalytic asymmetric synthesis. New York: VCH Publishers;
1993.
4. Noyori R. Asymmetric catalysis in organic synthesis. New York: Wiley
Interscience; 1994, and references therein.
5. Nogradi M. Stereoselective synthesis. New York: VCH Publishers;
1995.
6. Seyden-Penne J. Chiral auxiliaries and ligands in asymmetric synthe-
ses. New York: Wiley Interscience; 1995.
7. Whitesell JK. C2 symmetry and asymmetric induction. Chem Rev 1989;
89:15811590.
8. Noyori R. Chemical multiplication of chirality: Science and applica-
tions. Chem Soc Rev 1989;18:187198.
9. Noyori R, Takaya H. BINAP: An efficient chiral element for asymmet-
ric catalysis. Acc Chem Res 1990;23:345350.
10. Noyori R. Asymmetric catalysis by chiral metal complexes.
CHEMTECH 1992;22:360.
11. Noyori R. Asymmetric hydrogenation. Acta Chem Scand 1996;50:380
390.
12. Bennani YL, Hanessian S. Trans-1,2-Diaminocyclohexane derivatives
as chiral reagents, scaffolds and ligands for catalysis: Applications in
asymmetric synthesis and molecular recognition. Chem Rev 1997;97:
31613195.
13. Ohkubo K, Aoji T, Hirata K, Yoshinaga K. Molecular asymmetry in-
duced by usaturated additives in the enantioselective dehydrogenation
of racemic 1-phenylethanol by dichlorotris(triphenylphos-
phine)ruthenium (II) and (+)-neomenthyldiphenylphosphine. Inorg
Nucl Chem Lett 1976;12:837839.
14. Descotes G, Sabadie. Transfert catalytique dhydroge`ne. II. Emploi de
lalcool polyvinylique. J Bull Soc Chim Fr 1978;158162.
15. Descotes G, Martin JC, Sinou D, Dung T. Transfert catalytique
dhydroge`ne. III. Emploi de sucres insatures. Bull Soc Chim Fr
1979;6164.
16. Nishiguchi T, Tachi K, Fukuzumi K. Hydrogen transfer from dioxane
to an olefin catalyzed by chlorotris(triphenylphosphine) rhodium I. J
Am Chem Soc 1972;94:89168917.
17. Nishiguchi T, Fukuzumi K. Transfer-hydrogenation and transfer-
hydrogenolysis. III. Hydrogen transfer from dioxane to olefins cata-
lyzed by chlorotris(triphenylphosphine)rhodium I. J Am Chem Soc
1974;96:18931897.
18. Descotes G, Sinou D. Hydrogenation par transfert dhydroge`ne a` partir
des glucides. Reduction asymetrique de cetones insaturees prochi-
rales. Tetrahedron Lett 1976;45:40834086.
19. Parshall GW. Homogeneous catalysis. The applications and chemistry
of catalysis by soluble transition metal complexes. New York: Wiley
Interscience; 1980.
20. Yermakov YI. Selective hydrogenation of acetylenes to olefins cata-
lyzed by polymer-bound palladium (II) complexes. Catal Rev 1976;13:
7786.
21. Hartley FR, Vezey PN. Supported transition metal complexes as cata-
lysts. Adv Organomet Chem 1977;15:189234.
22. Holy NL. Ready hydrogenation of nitrobenzene and benzonitrile with
a ploymer-cound palladium catalyst. J Chem Soc Chem Commun
1978;10741075.
23. Brown JM, Molinari H. Supported rhodium-phosphine hydrogenation
catalyst of high mobility and reactivity. Tetrahedron Lett 1979;2933
2936.
24. Terasawa M, Yamamoto H, Kaneda K, Imanaka T, Teranishi SJ. Se-
lective hydrogenation of acetylenes to olefins catalyzed by polymer-
bound palladium (II) complexes. Catal 1979;57:315317.
25. Macdonald RP, Winterbottom JM. Palladium-polyamide catalysts for
419
the hydrogenation of some unsaturated hydrocarbons in the liquid
phase. J Catal 1979;57:195199.
26. Card RJ, Liesner CE, Neckers DC. Poly(styryl)bipyridinepalladium
complexes as heterogeneous catalyst for hydrogenation of alkenes and
alkynes. J Org Chem 1979;44:10951097.
27. Blaser HU. The chiral pool as a source of enantioselective catalysis and
auxiliaries. Chem Rev 1992;92:935952.
28. Augustine RL, Tanielyan SK, Doyle LK. Enantioselective heteroge-
neous catalysis I. A working model for the catalyst: modifier: substrate
interactions in chiral pyruvate hydrogenations. Tetrahedron: Asymme-
try 1993;4:18031827.
29. Brinker CH, Scherer GW. Sol-gel science. London: Academic Press;
1990.
30. Pajonk GM. Aerogel catalyst. Appl Catal 1991;72:217224 and refer-
ences therein.
31. Cauqui MA, Rodriguez-Izquierdo JM. Application of the sol-gel meth-
ods to a catalyst preparation. J Non-Cryst Solids 1992;147148:724738.
32. Schmidt H. Aspects of chemistry and chemical processing of organi-
cally modified ceramics. Mater Res Soc Symp Proc 1990;180:961973.
33. Sanchez C, Ribot F. Design of hybrid organic-inorganic materials syn-
thesized via sol-gel chemistry. New J Chem 1994;18:10071047.
34. Shea KJ, Loy DA, Webster OW. Aryl-bridged polysilsequioanesNew
microporous materials. Chem Mater 1989;1:572574.
35. Shea KJ, Loy DA, Webster OW. Arylsilsesquioxane gels and related
materials. New hybrids of organic and inorganic networks. J Am Chem
Soc 1992;114:67006710.
36. Corriu RJP, Moreau JJE, Thepot P, Wong Chi Man M. New mixed
organic-inorganic polymers: Hydrolysis and polycondensation of
bis(trimethoxysilyl)organometallic precursors. Chem Mater 1992;4:
12171224.
37. Corriu RJP, Moreau JJE, Thepot P, Wong Chi Man M. Hybrid silica
gels containing 1,3-butadiyne briding units. Thermal and chemical re-
activity of the organic fragment. Chem Mater 1996;8:100106.
38. Loy DA, Shea KJ. Bridged polysilsesquioanes. Highly porous hybrid
organic-inorganic materials. Chem Rev 1995;95:14311442.
39. Cerveau G, Chorro C, Corriu R, Lepeytre C, Le`re-Porte JP, Moreau
JJE, Thepot P, Wong Chi Man M. Hybrid organic-inorganic compos-
ites. In: Mark JE, Lee E-Y, Bianconi PA, editors. ACS Symp. Ser. 585.
Washington DC; 1995. p 210225.
40. Corriu RJP, Leclercq D. Recent developments of molecular chemistry
for sol-gel process. Angew Chem Int Ed Engl 1996;35:14201436.
41. Chevalier P, Corriu RJP, Moreau JJE, Wong Chi Man M. Chemistry of
hybrid organic-inorganic. Access to silica materials through chemical
selectivity. J Sol-Gel Sci Technol 1997;8:603607.
42. Boury B, Chevalier P, Corriu RJP, Delord P, Moreau JJE, Wong Chi
Man M. Hybrid organic-inorganic xerogel access to meso- and micro-
porous silica by thermal and chemical treatment. Chem Mater 1999;
11:281291.
43. Lim MH, Blanford CF, Stein A. Synthesis and characterization of a
reactive vinyl-functionalized MCM-41: Probing the internal pore struc-
ture by a bromination reaction. J Am Chem Soc 1997;119:40904091.
44. Macquarrie DJ. Direct preparation of organically modified MCM-type
materials. Preparation and characterisation of aminoproply-MCM and
2-cyanoethyl-MCM. Chem Commun 1996;19611962.
45. Burkett SL, Sims SD, Mann S. Synthesis of inorganic-organic meso-
porous silica by co-condensation of siloxane and organosiloxane pre-
cursors. Chem Commun 1996;13671368.
46. Schubert U. Catalysts made of organic-inorganic hybrid materials.
New J Chem 1994;18:10491058.
47. Schubert U, Hu sing N, Lorenz A. Hybrid inorganic-organic materials
by sol-gel processing or organofunctional metal alkoxides. Chem
Mater 1995;7:20122027.
48. Broudic J-C, Conocar O, Moreau JJE, Meyer D, Wong Chi Man M.
New hybrid silica based materials for the solid-liquid extraction of
actinides. J Mater Chem 1999;9:22832285.
49. Moreau JJE, Wong Chi Man M. The design of selective catalysts from
420 ADIMA ET AL.
hybrid silica-based materials. Coord Chem Rev 1998;178180:1073
1084.
50. Moreau JJE, Wong Chi Man M. Catalytic materials by design from
hybrid organic-inorganics. Mater Res Soc Symp Proc 1998;519:4150.
51. Adima A, Moreau JJE, Wong Chi Man M. Chiral organic-inorganic
solids as enantioselective catalytic materials. J Mater Chem 1997;7:
23312333.
52. Whitney TA. Direct optical resolution of trans-1,2-diaminocyclohexane
from an amine mixture. J Org Chem 1980;45:42144216.
53. Larrow JF, Jacobsen EN. A practical method for the large-scale prepa-
ration of [N,N-bis(3,5-ditertbutylsalicylidene)-1,2-cyclohexane-
diaminato(2-)]manganese(III) chloride, a highly enantioselective ep-
oxidation catalyst. J Org Chem 1994;59:19391942.
54. Corriu RJP, Guerin C, Moreau JJE. Stereochemistry at silicon. Top
Stereochem 1984;15:43198.
55. Corriu RJP, Leclercq D, Vioux A, Pauthe M, Phalippou J. Ultrastruc-
ture processing of advanced materials. In: Mackenzie JD, Ulrich DR,
editors. New York: Wiley; 1988. p 113117.
56. Maciel GE, Sindorf DW. Silicon-29 nuclear magnetic resonance study
of the surface of silica gel by cross-polarisation and magic-angle spin-
ning. J Am Chem Soc 1980;102:76067607.
57. Brunauer S, Emmett PH, Teller E. Adsorption of gases in multimo-
lecular layers. J Am Chem Soc 1938;60:309319.
58. Carpino LA, Knapczyk J, Mansour EME. Piperazino-functionalized
silica gel as a deblocking, scavenging agent for the 9-fluorenylmethy-
loxycarbonyl amino-protecting group. J Org Chem 1983;48:666669.
59. Soai K, Watanabe M, Yamamoto A. Enantioselective addition of dial-
kylzincs to aldehydes using heterogeneous chiral catalysts immobi-
lized on alumina and silica gel. J Org Chem 1990;55:48324835.
60. Ave W, Hastings CR. Preparation and chromatographic uses of sur-
face-bonded silicones. J Chromatog 1969;42:319336.
61. Gamez P, Fache F, Lemaire M. Enantioselective catalytic reduction of
ketones using C2-symmetric diamines as chiral ligands. Tetrahedron
Lett 1993;34:68976898.
62. Gamez P, Dunjic B, Fache F, Lemaire M. C2 diamine, pseudo-C2 poly-
(amide) and poly(urea) as chiral inductors in asymmetric catalysis. J
Chem Soc Chem Commun 1994;14171418.
63. Gamez P, Dunjic B, Pinel C, Lemaire M. Molecular imprinting effect
in the synthesis of immobilized rhodium complex catalyst (IRC cat).
Tetrahedron Lett 1995;36:87798782.
64. Gamez P, Fache F, Lemaire M. Asymmetric catalytic reduction of
carbonyl compounds using C2 symmetric diamines as chiral ligands.
Tetrahedron: Asymmetry 1995;6:705718.
65. Ter Halle R, Breheret A, Schulz E, Pinel C, Lemaire M. Chiral nitro-
gen-metal complexes for the asymmetric reduction of ketones. Tetra-
hedron: Asymmetry 1997;8:21012108.
66. Ohkuma T, Ooka H, Hashiguchi S, Ikariya T, Noyori R. Practical en-
antioselective hydrogenation of aromatic ketones. J Am Chem Soc
1995;117:26752676.
67. Hashigushi S, Fujii A, Takehara J, Ikariya T, Noyori R. Asymmetric
transfer hydrogenation of aromatic ketones catalyzed by ruthenium
(II) complexes. J Am Chem Soc 1995;117:76527653.
68. Gao J-X, Ikariya T, Noyori R. A ruthenium (II) complex with a C2-
symmetric diphosphine/diamine tetradentate ligand for asymmetric
transfer hydrogenations of aromatic ketones. Organometallics 1996;
15:10871089.
69. Pu ntener K, Schwink L, Knochel P. New efficient catalysis for enan-
tioselective transfer hydrogenations. Tetrahedron Lett 1996;37:8165
8168.