Adamantyl-BINOL as platform for chiral porous polymer aromatic frameworks. Multiple applications as recyclable catalysts

Article abstract of DOI:10.1016/j.jcat.2019.07.059

Herein, we report the synthesis of adamantyl-BINOL-based chiral porous aromatic polymers (Ad-BINOL-PAFs) for heterogeneous catalysis. Ad-BINOL-OH-PAF (365 m²·g^?1 SA_BET) was built through the covalent bonds among of 4,4′-dibromo-O-ethyl-protected adamantyl-BINOL with 1,3,5-Triphenylbenzene-4′,4″,4′″-triboronic acid and in the presence of [Ti(OiPr)₄] results an effective recyclable catalyst in the asymmetric addition of diethylzinc to aromatic aldehydes (ee up to 88%). The corresponding heterogenized phosphoric acid (Ad-BINOL-PO₂H-PAF) was applied as heterogeneous recyclable organocatalyst for the cascade condensation/amine addition of anthranilamide with aldehydes and transfer hydrogenation reactions obtaining high yields but low enantioselectivity. On the other hand, heterogeneous phosphoric acid (Ad-BINOLs-PO₂H-PAF) was also used as effective phosphate ligands for synthesis of rhodium(II) complexes which were effective catalysts in cyclopropanation of styrene affording chiral cyclopropanes in good yield and high diastereoselectivity (>99%) and moderate enantioselectivity (ee < 50%).

Full text of DOI:10.1016/j.jcat.2019.07.059

Journal of Catalysis 377 (2019) 609–618
Contents lists available at ScienceDirect
Journal of Catalysis
journal homepage: www.elsevier.com/locate/jcat
Adamantyl-BINOL as platform for chiral porous polymer aromatic
frameworks. Multiple applications as recyclable catalysts
d,
Cristina Monterde a,b, Rodrigo Navarro c, Marta Iglesias a, , Félix Sánchez
⇑
⇑
a Instituto de Ciencia de Materiales de Madrid, CSIC, c/ Sor Juana Inés de la Cruz, 3, Madrid, Spain
b Escuela internacional de Doctorado de la UNED, EIUNED, c/ Bravo Murillo 38, Madrid, Spain
c Instituto de Ciencia y Tecnología de Polímeros, ICTP-CSIC, c/ Juan de la Cierva, 3, Madrid, Spain
d Instituto de Química Orgánica, IQOG-CSIC, c/ Juan de la Cierva, 3, Madrid, Spain
a r t i c l e i n f o
a b s t r a c t
Article history:
Herein, we report the synthesis of adamantyl-BINOL-based chiral porous aromatic polymers (Ad-BINOL-
PAFs) for heterogeneous catalysis. Ad-BINOL-OH-PAF (365 m2ꢀgꢁ1 SABET) was built through the covalent
bonds among of 4,40-dibromo-O-ethyl-protected adamantyl-BINOL with 1,3,5-Triphenylbenzene-40,400,4
000-triboronic acid and in the presence of [Ti(OiPr)4] results an effective recyclable catalyst in the asym-
metric addition of diethylzinc to aromatic aldehydes (ee up to 88%). The corresponding heterogenized
phosphoric acid (Ad-BINOL-PO2H-PAF) was applied as heterogeneous recyclable organocatalyst for the
cascade condensation/amine addition of anthranilamide with aldehydes and transfer hydrogenation
reactions obtaining high yields but low enantioselectivity. On the other hand, heterogeneous phosphoric
acid (Ad-BINOLs-PO2H-PAF) was also used as effective phosphate ligands for synthesis of rhodium(II)
complexes which were effective catalysts in cyclopropanation of styrene affording chiral cyclopropanes
in good yield and high diastereoselectivity (>99%) and moderate enantioselectivity (ee < 50%).
Ó 2019 Elsevier Inc. All rights reserved.
Received 16 May 2019
Revised 24 July 2019
Accepted 31 July 2019
Available online 23 August 2019
Keywords:
Porous BINOL polymers
Heterogenized phosphoric acid
Transfer hydrogenation
BINOL phosphate rhodium
Microwave activation
1. Introduction
systems as the Jogensen–Hayashi catalyst or BINOL-derived phos-
phoric acid introduced into nanoporous polymeric networks
Porous organic polymers as covalent organic frameworks
(COFs) [1], hypercross-linked polymers (HCPs) [2,3], conjugated
microporous polymers (CMPs) [4], and polymers of intrinsic micro-
porosity (PIMs) [5], have been prepared from different building
blocks and have been applied for gas storage [6,7], catalysis [8–
12], sensors [13] and organic optoelectronics [14]. These materials
usually present excellent porosity properties (large surface area
and different networks) which allows them to accommodate dif-
ferent accessible catalytic centers and control their environment.
Many polymers have been obtained by anchoring of a monomer
to a polymer backbone [15,16]. The ‘‘bottom-up” approach is a
more effective strategy to heterogenize molecular catalysts in
comparison with the classical supported catalysts [17] and the
resulting porous polymers catalysts possess the catalytic centers
more accessible and homogeneously distributed [18]. There are
different examples of porous organic polymers (POPs) with cat-
alytic chiral sites, which act as heterogeneous catalysts combined
with a metal [19–24], and some examples of metal-free catalytic
[25,26] or COFs [27,28].
Herein, we report the easy and fast ‘‘bottom-up” designed syn-
thesis and characterization, of hindered BINOL-derivatives bearing
bulky groups embedded into a porous Polymeric Aromatic Frame-
work (PAF), and their application as catalysts for different reac-
tions. The chiral BINOL moieties were incorporated into the
network in three steps from the available reagents. The congested
soluble and heterogenized Ad-BINOLs-OH exhibit high catalytic
activity and enantioselectivity for the asymmetric addition reac-
tion of Et2Zn to benzaldehyde in combination with Ti(OiPr)4; the
BINOLs-PO2H show high activity for several reactions but moder-
ate chiral selectivity and the corresponding rhodium complexes
show moderate activity and selectivity for cyclopropanation of
styrene.
2. Results and discussion
2.1. Synthesis and characterization of porous aromatic frameworks
incorporating Ad-BINOL platforms (Ad-BINOL-OH-PAF)
⇑
Corresponding authors.
E-mail addresses: marta.iglesias@icmm.csic.es (M. Iglesias), felix-iqo@iqog.csic.
Enantiomeric pure BINOL (1,10-binaphth-2,20-diol) [29–34] and
its derivatives are important auxiliaries and ligands for asymmetric
es (F. Sánchez).
https://doi.org/10.1016/j.jcat.2019.07.059
0021-9517/Ó 2019 Elsevier Inc. All rights reserved.

610
C. Monterde et al. / Journal of Catalysis 377 (2019) 609–618
reactions and have been applied in different model reactions [35–
38]. BINOL skeleton was select as building block because it pre-
sents a structural rigidity which can contribute to the assembly
of the rigid PAF networks, and has available the 4-positions on
the naphthalene ring; these positions could be easily functional-
ized, by iodine or bromine, for further cross-coupling with boronic
acids to build the chiral framework.
be observed a band at 3529 cmꢁ1 corresponding to free O-H
(Fig. S60). 13C NMR spectrum shows signals at 150–110 ppm corre-
sponding to the aromatic carbons and three signals from adaman-
tyl aliphatic carbons at 45–25 ppm.
The porous properties measured by nitrogen adsorption/des-
orption isotherms at 77 k indicated that Ad-BINOL-OH-PAF is por-
ous with Brunauer-Emmett-Teller (BET) surface areas of
365.5 m2ꢀgꢁ1 (Fig. 1, Table 1). To evaluate the effect of substituents
on binaphthyl core on the porosity properties we prepared a 6,60-
Cl-substituted monomer and the corresponding polymer [40]
which has a BET surface area of 405.7 m2ꢀgꢁ1 and other with
methyl groups at 1,10-position instead of OEt groups (Ad-
Binaphthyl-Me in Scheme 1) with a BET of 196 m2ꢀgꢁ1 (Fig. 1).
Pore size distributions are shown in Fig. S70.
The synthesis of chiral polymer Ad-BINOL-OH-PAF and their
soluble counterpart Ad-BINOL-OH (D) is outlined in Scheme 1.
The precursor (B) was easily prepared at multigram scale from
commercially available (R)-BINOL and 1-adamantanol and charac-
terized by 1H and 13C NMR spectroscopy and mass spectrometry
[39]. Robust BINOL-frameworks (BINOL-PAFs) were prepared via
palladium-catalyzed Suzuki cross-coupling reaction between (R)-
4,40-dibromo-2,20-diethoxy-6,60-adamantyl (B) or chloro-1,10-
binaphthyl and the triboronic acid structural building block using
Pd(dppf)2Cl2 as catalyst under microwave heating (Scheme 1).
The resulting precipitate was filtered and washed several times
with water and treated with aqueous KCN for total removing of
palladium traces. The resulting precipitate was filtered and washed
several times with water and treated with aqueous KCN for total
removing of palladium traces. The ethoxy groups were deprotected
by treatment with BBr3 in CH2Cl2 affording Ad-BINOL-OH-PAF that
contain chiral dihydroxy groups. The polymers were obtained as
yellow powders insoluble in all the most common organic solvents
in quantitative yields. Following a similar method, we prepared a
soluble BINOL-OH, D (reference homogeneous catalyst) by a Suzuki
coupling between B and the phenylboronic acid followed by depro-
tection of the ethyl derivative C as shown in Schemes 1 and S2.
Details for characterization of soluble BINOL, D, can be found in
supplementary information. Ad-BINOL-OH-PAF was characterized
by 13C NMR, infrared spectroscopy (FT-IR), nitrogen adsorption,
etc. The IR spectra of Ad-BINOL-OH-PAF is consistent with the
incorporation of both monomers into the framework and it can
2.2. Catalytic applications
2.2.1. Diethylzinc addition to benzaldehyde
Ad-BINOL-OH-PAF was used as heterogenized BINOL ligand for
the formation of chiral catalysts by treating with excess Ti(OiPr)4
(Scheme 2). Resulting Ti-catalyst was applied for the addition of
diethylzinc to benzaldehyde and the results were compared with
that obtained from the corresponding soluble D-[Ti]-catalyst
(Table 2).
As shown in Table 2, when soluble D and heterogenized
Ad-BINOLs were treated with Ti(OiPr)4 are highly active catalytic
system in the addition of diethylzinc to benzaldehyde to afford
(R)-1-phenylpropan-1-ol. The reactions are quantitative conver-
sions and selective for the secondary alcohol. The enantiomeric
excess for the heterogenized catalyst was 88% similar to that
obtained with the corresponding soluble D-[Ti]. Compared with
other heterogenized systems, for example we found that
Ad-BINOL-O[Ti]-PAF gives better enantiomeric excess than
cross-linked polymers based on the 1,10-binaphthyl building
Scheme 1. Schematic preparation of embedded BINOL to porous aromatic framework.

C. Monterde et al. / Journal of Catalysis 377 (2019) 609–618
611
enantioselectivity (39.8%) (entry 8) [42]. However, when a 3-aryl
H8-BINOL was grafted on the surface of silica gel and the resulting
supported ligand was used in the alkylation of p-
chlorobenzaldehyde in the presence of Ti(OiPr)4 affords the corre-
sponding alcohol in high enantioselectivities and yields [43]. A
pillar[5]arene-based-TADDOL was also applied for the addition
reaction of ZnEt2 to benzaldehyde at ꢁ30 °C affording the (S)-1-
phenylpropan-1-ol in 88% yield and 94% ee after 48 h (entry 9)
[44]. A Cu-MOF with a chiral tetracarboxylate ligand derived from
1,10-bi-2-naphthol (CMOF) gives moderate selectivity towards the
alcohol (68%) and 82% ee after reacting overnight (entry 10) [45].
As can be concluded, Ad-BINOL-O[Ti]-PAF results an effective and
selective heterogeneous catalyst for the alkylation of benzaldehyde
at room temperature and 3 h reaction time.
160
140
120
100
80
60
40
Ad-Binaphthyl-Me-PAF
Ad-BINOL-OEt-PAF
Cl-BINOL-OEt-PAF
Ad-BINOL-OH-PAF
20
0
Concerning the mechanism of asymmetric ethylation of aldehy-
des catalyzed by a chiral ligand/Ti(OiPr)4 system, it appears that the
active species consists of a bimetallic titanium complex with a tita-
nium coordinated to the BINOLate ligand and the other with an alkyl
group ([BINOLate)Ti(aldehyde)(O-i-Pr)2]-[Ti(O-i-Pr)3Et] [46,47].
0,0
0,2
0,4
0,6
0,8
1,0
Relative Pressure (p/p°)
Fig. 1. Nitrogen adsorption isotherm of BINOLs-networks.
Table 1
Surface Areas and Pore Volumes of Ad-BINOL-PAFs.
2.2.1.1. Recycling. We have examined recyclability and reusability
of the Ad-BINOL-OH/Ti catalyst system. The solid was readily
recovered from the reaction mixture via centrifugation, followed
by repeated washing with HCl (1N), H2O, MeOH, THF and acetone.
The recovered catalyst was able to perform diethylzinc addition to
benzaldehyde for seven cycles without loss of conversion. During
the washing and recycling processes, residues of zinc and/or tita-
nium oxides could have been immobilized inside the material, this
would lead to a decrease in the enantioselectivity but not in the
conversion (Table 2, entries 3 and 4). Similar results were reported
previously a TADDOL-CPP catalyst [19] or a Cu-MOF [45].
Polymer
SABET
Pore volume
Pore size
(nm)
a
b
(m2ꢀgꢁ1
)
(cm3ꢀgꢁ1
)
Ad-BINOL-OEt-PAF
Ad-BINOL-OH-PAF
Cl-BINOL-OEt-PAF
Ad-Binaphthyl-Me-PAF
337
365
406
196
0.219
0.248
0.246
0.128
2.60
2.96
2.43
2.62
a
Calculated from the nitrogen adsorption isotherm.
At P/P0: 0.99.
b
blocks prepared via the trimerization reaction of terminal alkyne
groups for Lin et al. (entry 5) [21]. A BINOL supported on Zr-
phosphonate gives only 59% ee (Table 2, entry 6) [41] and a (R,
R)-tetraaryl-1,3-dioxolane-4,5-dimethanol (TADDOL)-based chiral
porous polymer gives similar ee (91%) although the reaction in this
case is done at ꢁ30 °C and 48 h reaction time (entry 7) [19].
Another example was reported when (R)-BINOL was incorporated
in the mesoporous framework of organosilicas (PMOs) and after
coordinating to Ti(OiPr)4, catalyze the asymmetric addition of
diethylzinc to benzaldehyde with high yields (99%) and moderate
2.3. Ad-BINOL-PO2H: Synthesis and characterization of porous
aromatic frameworks (Ad-BINOL-PO2H-PAF) and their corresponding
soluble phosphoric acids
With the Ad-BINOLs-OH in the hand, we have gone a step fur-
ther and prepared a series of phosphoric acids to be used as
organocatalysts and as ligands for rhodium(II) complexes.
Brønsted-acid catalysts are important organocatalysts for a great
number of carbon–carbon bond-forming reactions. Brønsted acids
are classified as neutral (thiourea and TADDOL) and stronger
Scheme 2. Formation of chiral-[Ti]-catalyst.

612
C. Monterde et al. / Journal of Catalysis 377 (2019) 609–618
Table 2
Asymmetric ethylation of benzaldehyde catalyzed by Ad-BINOL-[Ti].
Entry
Catalyst
Conv. (%)c (h)
ee (%)d
1
2
3
4
5
6
7
8
9
10
D-[Ti]a
91 (1)
100 (3)
50 (3)
87.0
88.0
35.4
65
68
59
91
39.8
94
Ad-BINOL-O[Ti]-PAFb
2run (without regeneration)
7run (after regeneration)
CCP-2 [21]
90 (3)
94 (16)
95 (16)
86 (48)
99 (2)
88 (48)
99 (overnight)
ZrL3 [41]
TADDOL-CPP [19]
MMB40-OTi [42]
TADP5 [44]
CMOF-3b [45]
82
a
b
c
D/[Ti]/Aldehyde/[Zn] (0.1/1.0/1.0/3.0), 1 h.
Ad-BINOL-O[Ti]/Aldehyde/[Zn] (20 mg/10/7.0/20), 3 h.
Determined by GC (dodecane as internal reference).
d
GC using a CP-Chirasil-Dex chiral column (100 °C 5 min; 2 °C/min to 130 °C); t1 (R) = 21.3 min; t2 (S) = 21.9 min [48].
Brønsted acids, such as phosphoric acids [49]. Chiral phosphoric
acids have attracted considerable attention in the preparation of
efficient chiral environments in organocatalysis and in transition
metal catalysis due to their Brønsted acid-base behavior, hydrogen
bonding, counter-anions and ligands toward metals [33,50–54].
BINOL-phosphoric acids are among the most important catalysts
being used for heterogeneous organocatalysis.
The heterogeneous and recyclable Ad-BINOL-phosphoric acid
(Ad-BINOL-PO2H-PAF) was prepared from the OH-material by
reaction with POCl3 followed by hydrolysis with aqueous H2SO4
(Scheme 3). The solid was thoroughly washed (HClaq., ethanol,
THF) to afford the acid polymer as an insoluble yellow powder.
Thermogravimetric analysis (Fig. S65) reveals its high thermal sta-
bility with decomposition temperature at 475 °C under a nitrogen
atmosphere. Solid-state CP/MAS 13C NMR spectroscopy shows
broad resonances peaks between 150 and 110 ppm, a peak at
146 ppm corresponds to the aryl carbons next to the oxygen atoms.
The peak centered at 127 ppm can be attributed to substituted aryl
carbons, and the aliphatic adamantyl groups appears at 43, 27 and
19 ppm (Fig. S62). The 31P NMR shows a signal centered at
3.83 ppm, at similar position that soluble phosphoric acid 5
(Fig. S63). The FT-IR spectra also indicate successful functionaliza-
tion (Fig. S64).
The porous properties were analyzed by nitrogen adsorption/
desorption isotherms at 77 k showing an isotherm characteristic
of microporous materials (Fig. 2, Table 3). The final phosphoric acid
derivative has a BET surface area of 248.0 m2ꢀgꢁ1; this fact indi-
cates that phosphorylation does not alter too much the porosity
properties of the material. Total pore volume result of 0.18 cm3
gꢁ1 at P/P0 = 0.99.
The morphology and texture was also studied by field-emission
scanning electron microscopy (SEM) showing the typical aggre-
gates of spherical structures described for this type of porous poly-
mers (Fig. 3).
We also have prepared a series of soluble bulky alkyl substi-
tuted R-BINOL-phosphoric acids (R-BINOLs-PO2H) (1–5 in
Scheme 4) from R-BINOLs-OH [39] by reaction with POCl3 followed
by hydrolysis to yield the corresponding enantiopure solid white
crystalline phosphoric acids in high yield (details in supporting
information).
Scheme 3. Schematic preparation of Ad-BINOL-PO2H-PAF.

C. Monterde et al. / Journal of Catalysis 377 (2019) 609–618
613
2.3.1. Catalytic application of soluble and heterogenized BINOL-
phosphoric acids
We have tested soluble (R-BINOL-PO2H) and heterogenized Ad-
BINOL-PO2H-PAF in a series of model organocatalyzed reactions.
160
140
120
100
80
2.3.1.1. Cyclization of anthranilamide with aldehydes. 2,3-
Dihydroquinazolinones are the family of compounds in which dif-
ferent substitutions displays important pharmacological, biological
and medicinal activity [55–59]. In addition, it has been reported
that their enantiomers have different bioactivities [60]. The 2,3-
disubstituted quinazolinones have been expected to have antiviral
and antihypertensive activities [56,61].
There are different synthetic methods to prepare these com-
pounds using catalysts as ionic liquids [62], [bmim]HSO4 [63],
some Brønsted acids [64], phosphoric acid [65,66], etc. These pro-
cedures present disadvantages such as harsh reaction conditions,
long reaction times, and poor yields beside the use of non-
recyclable and toxic catalysts associated with demands of develop-
ment of greener process involving easily available, easy to handle
and efficient catalysts. In this context, we reported the catalytic
performance of BINOL-phosphoric acids for the formation of dihy-
droquinazolinones by reaction of anthranilamide and benzaldehy-
des (Table 4). Soluble and heterogenized catalysts result effective
catalysts, we found excellent activity with quantitative yields;
however, only marginal ee’s were obtained. When precursor
BINOL-OH was the catalysts, we obtain selectively the imine (entry
9). The possible transition state for the cyclization reaction may be
as proposed for a SPINOL-phosphoric acid by Lin et al. [67].
60
Ad-BINOL-PO2H-PAF
Ad-BINOL-OH-PAF
40
0,0
0,2
0,4
0,6
0,8
1,0
Relative Pressure (p/p°)
Fig. 2. Nitrogen adsorption isotherm of Ad-BINOLs network.
Table 3
Porous properties.
Polymer
SABET
Pore volume
Pore size
(nm)
a
b
(m2ꢀgꢁ1
)
(cm3ꢀgꢁ1
)
Ad-BINOL-OH-PAF
Ad-BINOL-PO2H-PAF
365
248
0.25
0.18
2.72
2.96
a
BET surface area calculated from the nitrogen adsorption isotherm.
At P/P0: 0.99.
b
2.3.1.1.1. Recycling of solid catalyst Ad-BINOL-PO2H-PAF. The
heterogeneous Ad-BINOL-PO2H-PAF can be easily separated by
centrifugation and reused for further repeating runs. For each
run, >99% conversion was observed (see Table 5). The selectivity
decreases after five cycles yielding the imine. After a regeneration
process with HClO4 the selectivity to cyclic product was recovered.
Furthermore, we performed hot extraction experiments to check
the heterogeneity of catalyst. After 20% conversion of substrate,
we separated the catalyst, and even after 24 h no further conver-
sion was observed, which demonstrates that the catalyst is mainly
heterogeneous.
2.3.1.2. Transfer hydrogenation. To establish the versatility of these
easy available adamantyl-BINOL-PO2H catalysts, they were also
applied in a reaction type catalyzed by Brønsted acids: the transfer
hydrogenation [68] (Table 6). The substrates of choice are
N-Heterocycles [69] (2-phenylquinoline, 2-phenylbenzoxazine
and 2-phenylbenzothiazine) and as hydrogen source we use the
Hantzsch ester (diethyl 2,6-dimethyl-1,4-dihydropyridine-3,5-dic
arboxylate). As can be observed, high yields were obtained in short
reaction times with low enantiomeric excess. Lower temperatures
did not affect the selectivity but did decrease the product yield. It
can be observed that 2-phenylbenzothiazine is easily reduced
without poisoning of the catalyst.
Fig. 3. SEM image of Ad-BINOL-PO2H-PAF.
A possible mechanism will be similar to that described previ-
ously for transfer hydrogenation of benzoxazines and quinolones
[70,71]. First, the protonation of the cyclic imine by phosphoric
acid takes place giving a iminium-phosphate ion pair. Second,
hydride transfer from Hantzsch ester give the product and pyri-
dinium salt and finally a proton transfer close the cycle yielding
the Hantzsch pyridine.
2.4. Synthesis and characterization of tetrakis(binaphthyl-phosphate)
dirhodium(II,II) complexes
Chiral dirhodium complexes are effective catalysts for decompo-
sition of diazo compounds. Those complexes are generally obtained
Scheme 4. Synthesis of soluble R-BINOLs-PO2H.

614
C. Monterde et al. / Journal of Catalysis 377 (2019) 609–618
Table 4
Cyclization of anthranilamide with benzaldehydes.a
Entry
Catalyst
R
Conv. (%)b
Product
ee (%)b
1
2
3
4
5
6
7
8
1
2
3
4
H
H
H
H
H
H
OMe
Br
H
>99
>99
>99
>99
>99
>99
>99
>99
>99
99
E
E
E
E
E
E
E
E
F
E
1.3
8.3
0.6
4.2
2.3
10.1
12.0
13.0
–
5
Ad-BINOL-PO2H-PAF
9
Ad-BINOL-OH-PAF
CF3COOH
4d in [66]
10
11
12
H
H
H
–
26
6–93
67
90
4a-4g in [64]
cDetermined by HPLC using a Chiralcel-OD column.
a
BINOL-PO2H/Substrate (1:100), in CHCl3 at ꢁ20 °C, 24 h.
b
Determined by 1H NMR.
with four chiral ligands as carboxylates, imidates or biaryl
phosphates. The Rh2(biarylphosphate)4 complexes are prepared
by reaction of Rh2(OAc)4 with the corresponding hydrogen phos-
phate and used as chiral catalysts for different reactions [73–79].
Dirhodium complexes with substituents at the 3,30-positions of
the BINOL moiety are scarce [77] and it has been demonstrated
the importance of such substitution in chiral phosphoric acid catal-
ysis [80]. Herein we described the synthesis of a series of dirhodium
complexes with different substituents at 3,30- and 6,60-positions of
the BINOL to evaluate the effect of such groups on the reactivity
Table 5
Recycling of Ad-BINOL-PO2H-PAF.a
Run
Conversion (%)
Product
1
2
3
4
5
6
>99
>99
>99
>99
>99
>99
E
E
E
E
F
F
a
Binol-PO2H/Substrate (1:100), in CHCl3 at ꢁ20 °C, 24 h.
Table 6
Transfer hydrogenation reactions catalyzed by Adamantyl-BINOLs-PO2H.a
Entry
Catalyst
5
X
Solvent
T (°C)
Conv (%)b
ee (%)c
1
2
3
4
5
6
1
2
3
4
5
6
7
8
9
CH
CH
CH
CH
CH
CH
O
O
O
O
O
O
O
O
O
S
O
THF
THF
THF
THF
35
RT
35
ꢁ15
35
10
RT
RT
RT
RT
0
ꢁ78
RT
RT
RT
RT
RT
77.2
64.8
20.0
3.7
94.1
96.7
99 (80)d
99
99
99
99
99
19.5
19.8
41.9
36.0
15.0
22.0
31.4
34.5
24.4
23.0
34.6
35.6
12.7
15.1
2.5
2
Toluene
Toluene
CHCl3
CH2Cl2
Toluene
THF
CHCl3
CHCl3
CHCl3
CHCl3
CHCl3
CHCl3
CHCl3
2
1
5
99
99
PO2H-PAF
2
2
99
10
99d
73d
9.9
12.6
11e
a
b
c
Reaction conditions: substrate [72] (1.0 eq.), Hantzsch ester (1.25 eq.) catalyst (5%) in chloroform (2 mL).
Determined by GC and 1H NMR.
Determined by HPLC using a Chiralcel-OD column.
Isolated yield.
R = CN.
d
e

C. Monterde et al. / Journal of Catalysis 377 (2019) 609–618
615
desired complex was isolated in 50% yield. The effect of substitution
at the 3-position was examined using tri-adamantylbinaphthol (2)
as ligand, the corresponding 2-Rh-complex was prepared with
45% yield. Details of characterization data and NMR, FTIR and MS
spectra can be found in supplementary.
PAF-BINOL-PO2-dirhodium(II) complex was prepared as
described for soluble PO2-Rh complexes by refluxing the corre-
sponding PAF-binaphthyl phosphate with Rh2(OAc)4 in chloroben-
zene (see Scheme 6). The desired complex was isolated as a
greenish solid with an Rh loading of 1.5% (determined by ICP anal-
ysis). The molecular structure corresponds to a phosphate ligand
and the acetate ligands remains coordinated to rhodium as can
be observed in the 13C NMR spectrum (Fig. S66) with signals corre-
sponding to the aromatic carbons (between 151 and 115 ppm),
adamantyl groups (43.27, 36.69 and 29.33 ppm) and CH3 from
acetate at 23.65 ppm. 31P NMR shows a signal at 6.52 ppm
(Fig. S67). TGA (Fig. S69) shows the high thermal stability of this
complex (500 °C). Nitrogen adsorption/desorption isotherms at
77 k shows a decrease of surface area to 54 m2/g.
Scheme 5. Synthesis of soluble phosphate-dirhodium complexes.
and enantioselectivity for the enantioselective cyclopropanation of
styrene.
Dirhodium(II) complexes were prepared according to the
reported procedures by refluxing eight equivalents of correspond-
ing enantiopure (R)-binaphthyl phosphate with Rh2(OAc)4 in
chlorobenzene (Scheme 5) [73–79]. This method is an efficient
method for the introduction of bulky ligands because using a system
Soxhlet with sand and Na2CO3, the acetic acid is removed. The
2.4.1. Cyclopropanation of styrene
Preparation of cyclopropanes by catalytic enantioselective
methods have been of important pharmaceutical interest. With
Rh-complexes in hand, we evaluated their catalytic efficiency for
Scheme 6. Synthesis of dirhodium-polymer.
Table 7
Ad-BINOL-[Rh]-catalyzed-cyclopropanation of styrene.a
Entry
Catalyst
Ar
Conv. (%)b (h)
d.r.(%)b
ee (%)c
1
2
3
4
5
6
7
8
1-Rh
2-Rh
3-Rh
5-Rh
ClPh
100
97
96
91
90
85
74–82
89
97.8
97.7
98.0
98.0
99.0
–
48.9
37.2
49.9
17.9
12.0
40.0
23–43
57
Ad-BINOL-PO2-[Rh]-PAF
Rh2(R-BNP)4 [84]
1a, 2a, 2b [77]
Rh2(R-BNP)4 [81]
Ph
Ph
ClPh
–
a
b
c
Reaction conditions: styrene (1 eq.), 2-(4-chlorophenyl)-2-diazoacetate (1.5 eq.), toluene (1 mL), catalyst (1 mol% based on Rh).
Determined by GC (hexadecane as internal reference).
HPLC using a Chiralcel (OD) chiral column.

616
C. Monterde et al. / Journal of Catalysis 377 (2019) 609–618
the cyclopropanation of styrene with Cl-phenyldiazoacetate
(Table 7). Soluble catalysts have excellent reactivity (conversion
100% and 96%) and the cyclopropane was obtained as a single
diastereomer (>98:2 dr), these data are comparable to that
described previously for dibromobinaphtholphosphate-Rh-cata
lysts [76,77].
1, 3 and 5-Rh-catalysts afforded the cyclopropane in the same
predominant enantiomeric form (1S, 2R) [81,82]; however it is
important to note that 2-Rh (with an adamantyl group at
3-position) gives the contrary enantiomer.
Heterogeneous Ad-BINOL-PO2-[Rh]-PAF shows excellent reac-
tivity (conversion > 90%) and the cyclopropane was obtained as a
single diastereomer (99: 1 dr) with 13.7%.
The mechanism of PO2-Rh(II)-catalysed cyclopropanation
should be similar to that investigated computationally using
Rh2(formate)4 as a model [83].
3.4. Catalytic activity
Details for catalytic experiments are found in supplementary
information.
4. Conclusions
We have successfully prepared
a new embedded chiral
adamantyl-BINOL-polymer (365 m2/g SABET) which results highly
active and selective for the asymmetric addition of Et2Zn to ben-
zaldehyde (88% ee); these homochiral Ad-BINOL-PAFs materials
are stable, easily separable, and can be reused several times. The
Ad-BINOLs were easily converted into BINOL-phosphoric acids
which are effective Brønsted acid organocatalysts (soluble and
heterogeneous) and phosphate ligands to prepare rhodium(II)
complexes. The corresponding phosphate dirhodium complexes
were also applied as effective catalysts for cyclopropanation of
styrene affording chiral cyclopropanes in good yields with high
diastereoselectivity (>99%) and moderate enantioselectivity
(ee < 50%).
3. Experimental section
3.1. Synthesis of soluble BINOLs phosphoric acids (1–5)
Acknowledgements
The corresponding (R)-adamantyl-BINOL (1.0 eq.) [39] was dis-
solved in dry pyridine (2 mL) and then POCl3 (2.0 eq.) was added at
room temperature. The reaction mixture was stirred overnight;
then, water was added and the mixture stirred for 6 h and
extracted with dicloromethane and HCl (2 M) several times. The
organic layer was dried over Na2SO4 and the solvent eliminated
under vacuum to yield a solid (Yield 90%).
Authors acknowledge to MINECO of Spain (Project MAT2017-
82288-C2-2-P) for financial support.
Appendix A. Supplementary material
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.jcat.2019.07.059.
3.2. Adamantyl–BINOL-polymers (Ad-BINOL-PO2H-PAF)
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