Utilization of Donor–Acceptor Interactions for the Catalytic Acceleration of Nucleophilic Additions to Aromatic Carbonyl Compounds

Article abstract of DOI:10.1002/anie.201711726

A conceptually new method for the catalytic electrophilic activation of aromatic carbonyl substrates, by utilizing donor–acceptor interactions between an electron-deficient macrocyclic boronic ester host ([2+2]_BTH-F) and an aromatic carbonyl guest substrate, was realized. In the presence of a catalytic amount of [2+2]_BTH-F, dramatic acceleration of the nucleophilic addition of a ketene silyl acetal towards either electron-rich aromatic aldehydes or ketones was achieved. Several control experiments confirmed that inclusion of the aromatic substrates within [2+2]_BTH-F, through efficient donor–acceptor interactions, is essential for the acceleration of the reaction.

Full text of DOI:10.1002/anie.201711726

A Journal of the Gesellschaft Deutscher Chemiker
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Accepted Article
Title: Utilization of Donor-Acceptor Interaction for the Catalytic
Acceleration of the Nucleophilic Addition to Aromatic Carbonyl
Compounds
Authors: Tatsuhiro Uchikura, Kosuke Ono, Kohei Takahashi, and
Nobuharu Iwasawa
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To be cited as: Angew. Chem. Int. Ed. 10.1002/anie.201711726
Angew. Chem. 10.1002/ange.201711726
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10.1002/anie.201711726
Angewandte Chemie International Edition
COMMUNICATION
Utilization of Donor-Acceptor Interaction for the Catalytic
Acceleration of the Nucleophilic Addition to Aromatic Carbonyl
Compounds
Tatsuhiro Uchikura,[a] Kosuke Ono,[a,b] Kohei Takahashi,[a] and Nobuharu Iwasawa*[a]
Dedicated to Professor Teruaki Mukaiyama in celebration of his 90th birthday (Sotsuju).
Abstract: A conceptually new method for the catalytic electrophilic
Nu
donor-acceptor
interaction
activation of aromatic carbonyl substrates by utilizing donor-acceptor
interaction between an electron-deficient macrocyclic boronic ester
host ([2+2]BTH-F
) and aromatic carbonyl guest substrates was
electron-deficient
host
RC
O
CR
O
realized. In the presence of a catalytic amount of [2+2]BTH-F, dramatic
acceleration of the nucleophilic addition of ketene silyl acetal
towards electron-rich aromatic aldehydes or ketones was achieved.
Several control experiments confirmed that inclusion of aromatic
substrates in [2+2]BTH-F with efficient donor-acceptor interaction is
essential for the acceleration of the reaction.
aromatic substrate
“less reactive"
Included substrate
"more reactive"
Figure 1. Schematic representation of the concept of electrophilic activation of
aromatic carbonyl compounds by donor-acceptor interaction.
Addition of nucleophiles to carbonyl compounds is one of the
most fundamental reactions in organic synthesis. In the
conventional activation, Lewis acids are the most commonly
employed, and coordination of the lone pair of the carbonyl
group to a Lewis acid induces polarization of the carbonyl group,
enhancing its reactivity effectively.[1] Although these activation
methods are useful, development of a conceptually new mode of
activation of carbonyl compounds is highly desirable because
such a method would enable different reactivity and selectivity.
As such a new activation method, we thought of utilizing donor-
acceptor interaction[2] between an electron-deficient aromatic
host molecule and electron-rich aromatic carbonyl guest
substrates (Figure 1). Once an aromatic carbonyl substrate is
included in a highly electron-deficient host molecule, donor-
acceptor interaction between the host and guest aromatic
moieties is expected to decrease the electron density of the
guest aromatic moiety, which would lead to increase of the
electrophilicity of the conjugated carbonyl carbon. Here we
report the first example of a catalytic electrophilic activation of
aromatic carbonyl compounds upon inclusion inside electron-
deficient macrocyclic boronic ester. The addition of ketene silyl
acetal to electron-rich aromatic aldehydes or ketones is
accelerated in the presence of a catalytic amount of the host
molecule.
As a method for the preparation of an electron-deficient
aromatic host molecule, we employed macrocyclic boronic ester
formation developed in our laboratory.[3] The boronic esters can
easily be constructed by self-assembly of appropriate aryl
diboronic acids and indacene tetrol, and the two aryl planes
derived from the diboronic acid are situated in an ideal distance
for inclusion of one aromatic molecule by π-π interactions.[4] As
a
diboronic
acid
component,
5,6-difluorobenzo-
[c][1,2,5]thiadiazole unit was chosen, which has often been used
as a π electron acceptor for photovoltaic molecules and low
band-gap polymers.[5] The desired electron-deficient macrocyclic
boronic ester [2+2]BTH-F was obtained in high yield simply by
mixing equimolar amounts of 1 and racemic indacene tetrol 2 in
a
9:1 mixture of tert-butyl alcohol and toluene at room
temperature (Figure 2a).[6],[7] As an aromatic aldehyde, 2-
naphthaldehyde 3a was chosen and it was found to be included
in [2+2]BTH-F with an association constant of 157 M–1 in
dichloromethane. The X-ray diffraction analysis of the inclusion
complex 3a@[2+2]BTH-F revealed that the naphthyl moiety was
sandwiched by two difluorobenzothiadiazole units with 3.6 Å
distance in A-D-A manner (A: acceptor, D: donor) and the
aldehyde moiety was situated just outside of the host (Figure 2b).
Subsequent UV-vis study in the solid state of 3a@[2+2]BTH-F
showed a new absorption band at 380-420 nm, which was not
observed in free 3a or [2+2]BTH-F and thought to be derived from
donor-acceptor interaction between 3a and [2+2]BTH-F (Figure
2c). This donor-acceptor interaction is expected to induce
electrophilic activation of the carbonyl group of 3a. With the
promising result in the solid state, nucleophilic addition in
solution was examined by using ketene silyl acetal 4 as a
nucleophile (Table 1).[8] First, a 19.2 mM dichloromethane-d2
solution of 3a was treated with 1.05 equivalent of 4 in the
[a]
[b]
T. Uchikura, Dr. K. Ono, Dr. K. Takahashi, Prof. N. Iwasawa
Department of Chemistry, Tokyo Institute of Technology
O-okayama, Meguro-ku, Tokyo 152-8551 (Japan)
E-mail: niwasawa@chem.titech.ac.jp
Dr. K. Ono
presence of 0.1 equivalent of [2+2]BTH-F
. Based on the
Present address: Department of Chemistry, Faculty of Science,
Tokyo University of Science, Tokyo 162-8601 (Japan)
association constant, about 74% of [2+2]BTH-F included the
aldehyde at the initial state to give the host-guest complex
3a@[2+2]BTH-F
.
Supporting information for this article is given via a link at the end of
the document.
This article is protected by copyright. All rights reserved.

10.1002/anie.201711726
Angewandte Chemie International Edition
COMMUNICATION
S
additional 1 equivalent of naphthalene, the initial rate of the
reaction was reduced to about a half of the original reaction (kobs
= 9.3 × 10–3 M–1•s–1, entry 4, Table 1), which also supported that
host-guest interaction between 2-naphthaldehyde 3a and
[2+2]BTH-F is the origin of the acceleration.[11]
a
N
F
N
F
F
F
O
O
O
(HO)2B
B(OH)2
B
B
B
B
O
tBuOH - toluene
(9:1)
N
N
S
1
rt, 3 h
90%
F
F
O
O
O
+
O
N
N
HO
HO
S
[2+2]BTH-F
Table 1. Addition of ketene silyl acetal 4 to 2-naphthaldehyde 3a.[a]
OH
OH
Electron-deficient
macrocyclic boronic ester
rac-2
OTBS
c
b
[2+2]BTH-F
additive
OTBS
OEt
CHO
CO2Et
+
CD2Cl2
4
1.05 equiv.
25 ºC, 30 min
3a
5a
350
400
[c]
wavelength / nm
kobs
entry
[2+2]BTH-F
additive
conversion[b]
3a@[2+2]
⣔ิ
[2+2]
3
/ (10–6•M–1•s–1
2.2 × 104
7.2
)
BTH-F
⣔ิ
3a
⣔ิ
2
BTH-F
1
1
0.1 equiv.
none
34%
250
300
350
400
450
500
wavelength / nm
none
2
none
< 1.0%
S
N
N
Figure 2. Self-assembly of electron-deficient [2+2]BTH-F and its complex with 2-
naphthaldehyde 3a. a, Conditions for self-assembly of [2+2]BTH-F. b, Crystal
structure of 3a@[2+2]BTH-F in space-filling representation.[15] Solvents are
omitted for clarity. (5,6-difluorobenzo[c][1,2,5]thiadiazole unit, red; tetrol unit,
gray; 3a, purple; and aldehyde unit, orange) The aldehyde unit is marked with
a dotted circle. c, UV-vis spectra at the solid state of 3a@[2+2]BTH-F (red),
[2+2]BTH-F (green), and 3a (orange).
pinB
Bpin
none
3
4
<1.0%
22%
15
F
F
6
0.2 equiv.
0.1 equiv.
9.3 × 103
1.0 equiv.
After stirring the reaction mixture for 30 minutes at room
temperature, it was found that the reaction was accelerated
dramatically to give β–siloxyester 5a in 34% yield, whereas
almost no reaction proceeded without the catalyst (entries 1 and
2, Table 1). To evaluate the acceleration rate, observed initial
rates kobs of reactions with or without [2+2]BTH-F were measured
(less than 20% conversion for 3a),[9] and it was revealed that the
reaction was accelerated by the factor of about 3100 (kobs = 2.2
× 10–2 M–1•s–1 with [2+2]BTH-F, kobs = 7.2 × 10–6 M–1•s–1 without
[2+2]BTH-F).[10] It is noteworthy that the reaction proceeded with a
catalytic amount of [2+2]BTH-F and the catalyst remained without
any decomposition. Furthermore, the TBS protected product 5a
was the single detectable product, while the reaction using
BF3•OEt2 as a typical Lewis acid gave a mixture of several
products under similar conditions (Table S6; see Supporting
Information). Several control experiments were carried out to
confirm that the reaction is truly accelerated by the inclusion of
the aldehyde between two electron-deficient aromatic moieties.
First of all, the importance of [2+2]BTH-F structure was examined
by carrying out the reaction using monomeric pinacolate 6, and
a very small accelerating effect was observed, which supported
the necessity of macrocyclic structure (entry 3, Table 1). Since
no detectable interaction between 6 and 3a was observed by 1H
NMR, inclusion in the highly electron-deficient host [2+2]BTH-F is
essential for this activation. Acceleration by the Lewis acidity of
boron atoms could also be disregarded by this experiment.
Competitive inhibition experiment was also investigated by the
addition of naphthalene, which has almost the same association
constant (Ka = 103 M–1) with 3a (Ka = 157 M–1). When the same
reaction as shown in entry 1 was carried out in the presence of
[a] Performed with 3a (19 mM), 4 (20 mM) and [2+2]BTH-F (1.8 mM) in
CD2Cl2 (0.5 mL). [b] Conversion at 30 min was determined by 1H NMR. [c]
Observed rate constant (kobs) was estimated by time-dependent 1H NMR at
less than 20% conversion of 3a.
Next, to understand the characteristics of the activator
[2+2]BTH-F, substrate scope was examined by comparing the kobs
in the presence of [2+2]BTH-F or 6 (Table 2). The reactions of
electron-rich aromatic aldehydes 3b and 3c were highly
accelerated in the presence of 0.02–0.1 equiv. of [2+2]BTH-F
(ratio of kobs 3b: 1600 (0.02 equiv.of [2+2]BTH-F)
[12]; 3c: > 420 (0.1
equiv. of [2+2]BTH-F)). On the other hand, the acceleration of the
reaction with electron-deficient guest molecule 3d, which has a
similar Ka value to that of 3b, was greatly reduced (ratio of kobs
=
19).
These results strongly suggested the significance of the
donor-acceptor interaction between electron-rich guest
molecules and electron-deficient [2+2]BTH-F for the efficient
electrophilic activation. Even the reaction of ketone 3f was
accelerated to some extent (ratio of kobs = 21). Association
constant is also important. The reaction of benzaldehyde 3e
which has a small association constant (Ka = ~ 0 M–1) was not
accelerated effectively, supporting the importance of inclusion in
[2+2]BTH-F
.
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10.1002/anie.201711726
Angewandte Chemie International Edition
COMMUNICATION
Table 2. Addition of ketene silyl acetal 4 to various aldehydes 3a-e and
ketone 3f in the presence of a catalytic amount of [2+2]BTH-F or 6.[a]
Table 3. Application of the [2+2]BTH-F system.[a]
a
OTBS
CO2Et
CHO
OTBS
O
3
TBSO
R
X
additive
1.05 equiv. 4
+
CO2Et
OEt
4
R
X
additive
3a
5a
CD2Cl2
25 ºC
5
+
F
+
CD2Cl2
25 ºC
F
F
F
F
F
OTBS
F
F
CHO
F
F
F
R
CO2Et
R =
[c]
kobs
ratio of
5g
Ka[b]/M–1
additive
[d]
/ (10–6•M–1•s–1
)
kobs
F
CO2Et
substrate
F
F
7g
3g
2.2 × 104
CHO
[2+2]BTH-F
6
yield[b]
157 ± 6
1500
1600[e]
> 420
15
3a
additive
none
time
5a
5g+7g (ratio)
Me
N
[2+2]BTH-F
6
1.9 × 104[e]
125 h
14 h
4.7%
77% (77 : 0)
CHO
97.5 ± 2.8
47.7 ± 4.7
12[e]
0.1 equiv. [2+2]BTH-F
82%
9.3% (2 : 7)
3b
[2+2]BTH-F
6
> 3.5 × 104
CHO
S
S
S
S
83
3c
CHO
[2+2]BTH-F
6
2.2 × 102
RO
X
b
CO2Et
76.2 ± 6.8
20
F
11
OHC
3d
O
2.1 equiv. 4
3
3
R = TBS : 9
R = H : 10
additive
X
CHO
O
[2+2]BTH-F
6
40
20
+
OHC
CD2Cl2, 25 ºC
~ 0[f]
2.0
3
OH
X
8
3e
EtO2C
11
O
[2+2]BTH-F
6
1.4 × 102
yield[b]
86.5 ± 6.0
21
6.6
substrate
additive
time
24 h
9+10 (ratio)
11
3f
0.1 equiv.
[a] Performed with 3 (19 mM), 4 (20 mM) and [2+2]BTH-F (1.8 mM) or 6 (3.6
mM) in CD2Cl2 (0.5 mL). [b] Association constants (Ka) with [2+2]BTH-F were
determined by ITC study. [c] Observed rate constant (kobs) was estimated
by time-dependent 1H NMR at less than 20% conversion of 3a. [d] Ratio of
kobs was calculated by kobs([2+2]BTH-F) divided by kobs (6). [e] 0.02 equiv. of
[2+2]BTH-F and 0.04 equiv. of 6 were employed. [f] The association constant
was too small to be measured by ITC.
72% (72 : 0)
< 1.0%
[2+2]BTH-F
8a
(X = H)
0.4 equiv.
BF3•OEt2
3 h
48 h
1 h
18% (15 : 3)
71% (71 : 0)
< 1.0%
13%
<1.0%
79%
[c],[d]
0.1 equiv.
[2+2]BTH-F
8b
(X = Me)
0.4 equiv.
[c]
BF3•OEt2
To show the unique character of this activation method,
several applications were examined. Firstly, selective activation
of electron-rich aromatic aldehyde in the presence of electron-
poor one was examined (Table 3a). In the absence of [2+2]BTH-F
,
electron-poor, fluorinated aromatic aldehyde 3g was more
reactive than 3a and treatment of a 1 : 1 mixture of 3a and 3g
with 4 (1.05 equiv. to 3a) afforded 5g in 77% yield as the major
product. On the contrary, when a 1:1 mixture of 3a and 3g was
treated with 4 in the presence of a catalytic amount of [2+2]BTH-F
,
the selective activation of electron-rich aromatic aldehyde 3a
occurred and product 5a was obtained in high yield (82%). Thus,
complete switching of reactive substrate was successfully
realized by the presence or absence of [2+2]BTH-F
.
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10.1002/anie.201711726
Angewandte Chemie International Edition
COMMUNICATION
the catalytic nucleophilic addition effectively. Control
experiments clearly indicated that inclusion of the aryl carbonyl
compounds in the internal space of [2+2]BTH-F is essential for the
activation and catalytic reaction. Activation of guest molecules
through donor-acceptor interaction will open up new possibilities
in the field of supramolecular catalysis.
TBSO
nBu
c
CO2Et
1.05 equiv. 4
O
additive
(Z): 13Z, (E): 13E
CD2Cl2
nBu
TBSO
CO2Et
rt, 24 h
12
nBu
14
Acknowledgements
yield[b] (initial rate / 10–10•M•s–1
)
This work was supported by a CREST project from the JST and
JSPS KAKENHI Grant Number 15H05800.
additive
0.1 equiv. [2+2]BTH-F
0.2 equiv. 6
13Z
13E
14
24% (564)
2.6% (28.9)
4.7% (88.6)
< 1.0% (5.8)
4.2% (75.9)
< 1.0% (6.0)
Keywords: Supramolecular catalyst• Donor-acceptor systems •
Host-guest systems • Electrophilic activation
[a] See SI for the details of the reaction procedures. [b] The yields were
determined by 1H NMR. [c] Products which reacted with both carbonyl
moieties were detected. [d] 1.05 equiv. of 4 was employed.
[1]
[2]
J. Matsuo, M. Murakami, Angew. Chem. Int. Ed. 2013, 52, 9109–9118;
Angew. Chem. 2013, 125, 9280-9289.
(a) R. Foster, J. Phys. Chem. 1980, 84, 2135–2141. (b) S. V. Rosokha,
J. K. Kochi, Acc. Chem. Res. 2008, 41, 641–653. (c) L. Emmett, G. M.
Prentice, G. Dan Pantoş, Annu. Rep. Prog. Chem., Sect. B: Org. Chem.
2013, 109, 217–234. (d) A. Das, S. Ghosh, Angew. Chem. Int. Ed. 2014,
53, 2038–2054; Angew. Chem. 2014, 126, 2068-2084.
Secondly, to show the intramolecular selectivity, the
nucleophilic addition to dicarbonyl substrates 8 was investigated
(Table 3b). Addition of ketene silyl acetal 4 to dialdehyde 8a in
the presence of a catalytic amount of [2+2]BTH-F solely gave 9a
where the conjugated carbonyl selectively reacted. In contrast,
both aldehyde moieties reacted equally to give a mixture of 9a,
10a and 11a by using BF3•OEt2 as a conventional Lewis acid.[13]
Furthermore, by using [2+2]BTH-F, perfect selective activation of
aromatic ketone in the presence of aliphatic aldehyde was
achieved when 8b was employed. In the presence of 0.1
equivalent of [2+2]BTH-F, the addition reaction occurred at the
ketone moiety selectively to give 9b in 71% yield. On the other
hand, in the presence of 0.4 equivalent of BF3•OEt2, only the
aldehyde moiety reacted to give 11b in 79% yield. This is a very
rare example for selective activation of ketone in the presence of
aldehyde.[14]
[3]
[4]
N. Iwasawa, H. Takahagi, J. Am. Chem. Soc. 2007, 129, 7754–7755.
Y. Kikuchi, H. Takahagi, K. Ono, N. Iwasawa, Chem. Asian. J. 2014, 9,
1001–1005.
[5]
(a) H. Zhou, L. Yang, A. C. Stuart, S. C. Price, S. Liu, W. You, Angew.
Chem. Int. Ed. 2011, 50, 2995–2998; Angew. Chem. 2011, 123, 3051-
3054. (b) N. Wang, Z. Chen, W. Wei, Z. Jiang, J. Am. Chem. Soc. 2013,
135, 17060–17068. (c) L. Dou, C. -C. Chen, K. Yoshimura, K. Ohya, W.
-H. Chang, J. Gao, Y. Liu, E. Richard, Y. Yang, Macromolecules 2013,
46, 3384–3390.
[6]
[7]
Screening of conditions for self-assembly of [2+2]BTH-F was shown in
Table S1 (See Supporting Information).
The obtained [2+2]BTH-F contained one molecule each of toluene and
tBuOH. These solvents couldn’t be removed even under high vacuum.
This solvent-containing [2+2]BTH-F was employed in the following
reactions. The solvents, however, had almost no effects on the
reactions (Table S2; See Supporting Information).
[8]
[9]
Screening of nucleophiles was shown in Table S3 (See Supporting
Information).
Finally, the Michael addition of ketene silyl acetal 4 was also
examined. In the presence of 0.1 equivalent of [2+2]BTH-F, enone
12 was found to react with 4 to give Michael adduct 13 about 20
times faster than in the presence of 0.2 equivalent of 6 (Table
3c).
The rate constant was estimated at less than 20% conversion due to
partial inhibition by the product 5a in the later stage of the reaction
(Table S4; see Supporting Information).
[10] Kinetic measurement by saturation method was not possible due to an
inhibition effect by a large excess of 4 (Table S5; see Supporting
Information).
[11] Preliminary DFT analyses of 3a, 3a@[2+2]BTH-F
, and its deviated
So far, several organic reactions have been catalyzed by a
catalytic amount of self-assembled anionic or cationic
coordination cages, or hydrogen-bonded capsules.[15] In these
cases, host molecules play crucial roles chiefly in providing the
isolated cavities for high local concentration of guest substrates,
preorganization of substrates into reactive conformations, or
stabilization of intermediate to promote target reactions.
Compared with these pioneering examples, the present host
molecule not only works as a reaction vessel but also activates
the substrates directly.
derivative revealed that LUMO of the carbonyl of 3a was lowered by
inclusion (Table S17; See Supporting Information).
[12] In the presence of 0.1 equiv. of [2+2]BTH-F, 3b reacted so rapidly that
the kobs could not be determined accurately (almost quantitative yield
(97%) within 30 minutes).
[13] When 4 was mixed with an equimolar mixture of 3a and heptanal, 3a
selectively reacted in the presence of [2+2]BTH-F (Table S11; see
Supporting Information).
[14] There are several reports of selective reduction of ketone in the
presence of aldehyde by in situ protection of aldehyde moiety. For
examples see; (a) J. -L. Luche, A. L. Gemal, J. Am. Chem. Soc. 1979,
101, 5848–5849. (b) M. P. Paradisi, G. P. Zecchini, G. Ortar,
Tetrahedron Lett. 1980, 21, 5085–5088. (c) R. Ohta, H. Fujioka, Chem.
Pharm. Bull. 2017, 65, 10–18.
In summary, donor-acceptor interactions between the
aromatic moieties of the host catalyst and the guest substrate is
utilized for the catalytic electrophilic activation of aryl carbonyl
compounds for the first time.[16] Inclusion in the highly electron-
deficient [2+2]BTH-F activates the aryl carbonyl compounds for
[15] (a) M. Yoshizawa, J. K. Klosterman, M. Fujita, Angew. Chem. Int. Ed.
2009. 48, 3418–3438; Angew. Chem. 2009, 121, 3470-3490. (b) M.
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10.1002/anie.201711726
Angewandte Chemie International Edition
COMMUNICATION
Raynal, P. Ballester, A. Vidal-Ferran, P. W. N. M. van Leeuwen, Chem.
Soc. Rev. 2014, 43, 1660–1733. (c) C. J. Brown, F. D. Toste, R. G.
Bergman, K. N. Raymond, Chem. Rev. 2015, 115, 3012–3035. (d) Q. -
Q. Wang, S. Gonell, S. H. A. M. Leenders, M. Dürr, I. Ivanović-
Burmazović, J. N. H. Reek, Nat. Chem. 2016, 8, 225–230. (e) Q. Zhang,
L. Catti, J. Pleiss, K. Tiefenbacher, J. Am. Chem. Soc. 2017, 139,
11482–11492. (f) J. K. M. Sanders, Chem. Eur. J. 1998, 4, 1378-1383.
(g) J. A. A. W. Elemans, E. J. A. Bijsterveld, A. E. Rowan, R. J. M.
Nolte, Chem. Commun. 2000, 2443-2444.
[16] For examples of acceleration reaction by utilizing non-covalent
interaction such as cation-π or anion-π interaction. (a) C. R. Kennedy,
S. Lin, E. N. Jacobsen, Angew. Chem. Int. Ed. 2016, 55, 12596–12624;
Angew. Chem. 2016, 128, 12784-12814 (b) Y. Cotelle, S. Benz, A. -J.
Avestro, T. R. Ward, N. Sakai, S. Matile, Angew. Chem. Int. Ed. 2016,
55, 4275–4279; Angew. Chem. 2016, 128, 4347-4351
[17] CCDC 1531359 (3a@[2+2]BTH-F
)
contains the supplementary
crystallographic data for this paper. This data is provided free of charge
by The Cambridge Crystallographic Data Centre.
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10.1002/anie.201711726
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Entry for the Table of Contents (Please choose one layout)
Layout 1:
COMMUNICATION
New type of supramolecular
Tatsuhiro Uchikura, Kosuke Ono, Kohei
Takahashi, Nobuharu Iwasawa*
catalyst: A conceptually new method
for the catalytic electrophilic activation
of aromatic carbonyl substrates by
utilizing donor-acceptor interaction
between an electron-deficient
macrocyclic boronic ester host
([2+2]BTH-F) and aromatic carbonyl
guest substrates was realized.
Page No. – Page No.
Utilization of Donor-Acceptor
Interaction for the Catalytic
Acceleration of the Nucleophilic
Addition to Aromatic Carbonyl
Compounds
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