Catalytic cross-coupling of diazo compounds with coinage metal-based catalysts: An experimental and theoretical study

Article abstract of DOI:10.1039/c2dt32439c

We examined the ability of Tp^xM (Tp^x = hydrotris(pyrazolyl)borate ligand; M = Cu and Ag) and IPrMCl (IPr = 1,3-bis(diisopropylphenyl)imidazol-2-ylidene; M = Cu, Ag, Au) complexes as catalyst precursors for the cross-coupling of diazo compounds. Experimental data showed that the metal centre can be tuned with the appropriate selection of the ligand to yield either the homo- or hetero-coupling (cross-coupling) products. A computational study of the reaction mechanism allowed the rationalization of the experimental reactivity patterns, and the identification of the key reaction step controlling the selectivity: the initial reaction between the metallocarbene intermediate and one of the diazo compounds.

Full text of DOI:10.1039/c2dt32439c

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An international journal of inorganic chemistry
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Volume 42 | Number 12 | 28 March 2013 | Pages 4093–4320
Featuring the themed issue: Mechanistic organometallic chemistry
ISSN 1477-9226
COVER ARTICLE
M. Mar Díaz-Requejo, Feliu Maseras, Pedro J. Pérez et al.
Catalytic cross-coupling of diazo compounds with coinage metal-based
catalysts: an experimental and theoretical study
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PAPER
Catalytic cross-coupling of diazo compounds with
coinage metal-based catalysts: an experimental and
Cite this: Dalton Trans., 2013, 42, 4132
theoretical study†
Ivan Rivilla,a W. M. C. Sameera,b Eleuterio Alvarez,c M. Mar Díaz-Requejo,*a
Feliu Maseras*b,d and Pedro J. Pérez*a
We examined the ability of TpxM (Tpx = hydrotris(pyrazolyl)borate ligand; M = Cu and Ag) and IPrMCl
(IPr = 1,3-bis(diisopropylphenyl)imidazol-2-ylidene; M = Cu, Ag, Au) complexes as catalyst precursors for
the cross-coupling of diazo compounds. Experimental data showed that the metal centre can be tuned
with the appropriate selection of the ligand to yield either the homo- or hetero-coupling (cross-coupling)
products. A computational study of the reaction mechanism allowed the rationalization of the experi-
mental reactivity patterns, and the identification of the key reaction step controlling the selectivity: the
initial reaction between the metallocarbene intermediate and one of the diazo compounds.
Received 12th October 2012,
Accepted 21st December 2012
DOI: 10.1039/c2dt32439c
www.rsc.org/dalton
Introduction
The metal-catalyzed carbene transfer reaction of diazo com-
pounds has constituted a useful methodology in organic syn-
thesis, both in inter- and intramolecular fashions.1 During
this reaction, unsaturated fragments can be modified upon
addition of a CR1R2 fragment to yield three member rings
(Scheme 1). Also, saturated X–Y bonds can be functionalized,
affording the corresponding insertion products.
The main drawback of all these reactions consists of the
non-desired side-reaction that originates from the coupling of
the metallocarbene intermediate with a second molecule of
the diazo reagent (Scheme 1). Further, this homocoupling
reaction is favoured over the addition/insertion processes,
although the use of a low diazo concentration usually pre-
cludes such coupling. Several groups have explored this re-
action as an alternative synthetic route for olefin synthesis,
Scheme 1 Metal-catalyzed carbene transfer reactions.
where the coupling of two fragments always derives from
the same diazo reagent. The ruthenium-based systems were
the commonly used catalysts for this transformation,2 and the
transition metals from groups 4–63 and 9–11 have also been
employed.4 Hodgson and co-workers described5 the cross-
coupling of two diazoacetates of formulae N2C(H)CO2R with
different R groups. But it was not until very recently that
Davies and co-workers have described a rhodium-based cata-
lytic system to promote the efficient cross-coupling of two dis-
tinct diazo compounds6 with a very high regioselectivity
toward the E isomer [eqn (1)].
aLaboratorio de Catálisis Homogénea, Departamento de Química y Ciencias de los
Materiales, Unidad Asociada al CSIC, Centro de Investigación en Química Sostenible
(CIQSO), Universidad de Huelva, Campus de El Carmen s/n, 21007 Huelva, Spain.
E-mail: perez@dqcm.uhu.es, mmdiaz@dqcm.uhu.es; Fax: +34-959219942
bInstitute of Chemical Research of Catalonia (ICIQ), 43007 Tarragona, Catalonia,
Spain. E-mail: fmaseras@iciq.es; Fax: (+34) 977 920 231
cInstituto de Investigaciones Químicas, Centro de Investigaciones Isla de La Cartuja,
Avda Americo Vespucio 49, 41092 Sevilla, Spain
dDepartament de Química, Universitat Autònoma de Barcelona, 08193 Bellaterra,
Catalonia, Spain
†Electronic supplementary information (ESI) available: Crystallographic data for
compound 4 (CIF). Conformational analysis of selected structures. Evaluation of
ð1Þ
steric/electronic effects through ONIOM calculations. Total energies and Carte-
sian coordinates of all reported structures. CCDC 905569. For ESI and crystallo-
graphic data in CIF or other electronic format see DOI: 10.1039/c2dt32439c
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We have described several catalytic systems based on the heterocoupling olefin (3) with both Z and E isomers. As shown
group 11 metal complexes for the addition7 or insertion8 of in Table 1, the copper-based catalysts exclusively afforded a
CHCO2Et (derived ethyl diazoacetate, EDA) to organic sub- mixture of diethyl fumarate and maleate (i.e., the homo-
strates. In view of the interest on the above cross-coupling re- coupling products from EDA). Neither of the other homo-
action, we have studied the potential of our catalysts (TpxM and coupling olefin 2 nor the heterocoupling 3 were detected at the
IPrMCl; Tpx = hydrotris(pyrazolyl)borate ligand; IPr = N-hetero- end of the reaction, and diazo compound B was recovered. In
cyclic carbene ligand) in this transformation, where we have contrast, the analogous silver-based complexes gave 90% of
found that both the copper and silver can be tuned with ligands the targeted cross-coupling product 3, whereas the homo-
to afford the formation of desired olefins. Theoretical calcu- coupling derivatives 1 and 2 were not formed. Different E : Z
lations were carried out to rationalize the mechanistic details.
regioselectivities were induced by both silver catalysts (Table 1,
entries 4, 5). Interestingly, a minor product was also formed in
this case, and was identified as an azine (4) that formally
derived from the coupling of two molecules of diazo com-
pound B after the loss of a molecule of N2. Yet described,10
we have unambiguously characterized compound 4 by compar-
ing the literature data as well as by X-ray diffraction studies
Results and discussion
Catalyst screening for the cross-coupling reaction of diazo
compounds
Previous work carried out in our laboratory has shown that (see ESI†).
two families of group 11 metal-based catalysts containing
After these findings, we wonder if the complexes IPrMCl
hydrotris(pyrazolyl)borate (Tpx) or N-heterocyclic carbene (IPr = 1,3-bis(diisopropylphenyl)imidazol-2-ylidene; M = Cu, Ag
(NHC) ligands (Scheme 2) readily transferred carbene units : and Au) could be also active for the reaction shown in eqn (2),
CHCO2Et from ethyl diazoacetate (EDA, N2CHCO2Et) to several given their already commented capabilities for carbene trans-
saturated or unsaturated substrates.7–9 The catalytic coupling fer from EDA.8a,b,11 Table 2 summarizes the results that we
of two carbene groups was observed as a side reaction, and have obtained. From which, the following information can be
this process could be avoided by slow addition of EDA. The extracted: (i) a halide scavenger (NaBAr′4 (Ar′ = 3,5-bis(trifluoro-
aforementioned work by Davies and co-workers6 guided us to methyl) phenyl)) is required for the reaction to occur with the
explore the catalytic potential of these compounds toward the Cu- and Ag-based catalysts; (ii) the gold complex remained
coupling of two different diazo compounds with the aim of catalytically inactive with and without such a scavenger. With
inducing the synthesis of the olefin derived from the cross- copper (Table 2, entry 2), homocoupling of EDA was observed
coupling of both carbenes.
as the minor product, while the cross-coupling product, 3, was
In the first series of experiments, we tested the catalytic obtained as the main product (89%). A similar result was
activity of several Tpx-containing complexes in the cross- observed with the silver analogue, but with the lack of 1.
coupling reaction of two different diazo compounds, EDA [A in
eqn (2)] and ethyl 2-phenyldiazoacetate [B in eqn (2)].
Table 1 Cross-coupling of diazo compounds A and B catalysed by TpxM (M =
Cu, Ag)a
Entry
Catalyst
1 : 2 : 3 : 4 (%)
E : Z (3)
1b
2b
3b
4
TpBr3Cu
TpPhCu
CuI
100 : 0 : 0 : 0
100 : 0 : 0 : 0
100 : 0 : 0 : 0
0 : 0 : 90 : 10
0 : 0 : 90 : 10
—
—
—
78 : 22
58 : 42
ð2Þ
Tp*,BrAg
TpBr3Ag
5
a Reaction conditions: 0.0125 mmol catalyst; 5 mL CH2Cl2; 0.25 mmol
of each diazo compound at 5 °C. b The diazo compound B remained
unreacted in the reaction mixture.
We could expect the formation of three olefins: those that
are coming from the homocoupling (1, 2) and the targeted
Table 2 Cross-coupling of diazo compounds A and B using IPrMCl (M = Cu, Ag
and Au) as a precatalysta
Entry
Catalyst
1 : 2 : 3 : 4 (%)
E : Z (3)
1
2
3
IPrCuCl
—
—
76 : 24
—
80 : 20
—
IPrCuCl + NaBAr′4
IPrAgCl
5 : 0 : 89 : 6
—
0 : 0 : 91 : 9
—
4
IPrAgCl + NaBAr′4
IPrAuCl + NaBAr′4
5b
a Reaction conditions: 0.0125 mmol catalyst; 5 mL CH2Cl2; NaBAr′4
(1 equiv.); 0.25 mmol diazo compounds at
°C. b Both diazo
compounds remain unreacted in the reaction mixture.
5
Scheme 2 Ligands employed in this work.
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Again, homocoupling of the diazo compound B (i.e., olefin 2)
was not detected. The E : Z ratio of 3 was similar with both
metals (entries 2 and 4), indicating a similar catalytic pocket.
The azine, 4, was also formed to a similar extent to that in the
TpxM system. It is worth mentioning that the experiments
were carried out upon addition of the diazo compounds in one
portion at the beginning of the reaction.
The optimized results shown in Tables 1 and 2 were
obtained at 5 °C, and no significant reaction outcome was
observed below this temperature. When the reactions were
carried out at room temperature (23 °C) with Tp*,BrAg and
IPrAgCl as catalyst precursors, the 1 : 2 : 3 : 4 ratio of products
found at the end of the reaction was 0 : 0 : 57 : 43 and
0 : 0 : 47 : 53, respectively. Further, both catalysts provide a sig-
nificant increase of the azine, 4. The E/Z selectivity did not
change with the temperature.
The above experimental data have shown that TpxAg and
IPrMCl (M = Cu and Ag) complexes are active catalysts for the
cross-coupling reaction of N2C(H)CO2Et and N2C(Ph)CO2Et to
afford the desired heterocoupling-derived olefins 3. Further,
this is the first example of group 11 metal-based catalysts for
this reaction at those levels of efficiency. A minor product was
identified as the azine (4). On the other hand, the TpxCu
system exclusively led to the homocoupling products, 1. There-
fore, there is a clear effect of the ligand (Tpx vs. IPr) in the
copper case as well as an effect of the metal, Cu vs. Ag, in the
Tpx case. In order to ascertain the nature of the mechanism
that governs this transformation, a complete theoretical study
has been carried out with both the TpBr3M (M = Cu, Ag) and
IPrMCl systems (M = Cu, Ag, Au), which is the subject of the
next section.
Scheme 3 Proposed catalytic cycle for the reaction of N2C(Ph)CO2Et (6a) and
N2C(H)CO2Et (6b) catalyzed by TpxM (M = Ag, Cu).
TpBr3Ag. Results are summarized in Scheme 4A. Coordination
of 6a and 6b on TpBr3Ag is endergonic by +9.5 (7a) and +5.0
(7b) kcal mol−1, respectively. The key step happens to be the
subsequent N2 elimination from 7a, leading to the metallo-
carbene 8a through transition state TS1a with a relative energy
of 19.8 kcal mol−1. In a similar vein, the second metallo-
carbene, 8b, can be formed through TS1b with a relative energy
of 22.0 kcal mol−1. This step is critical because it constitutes the
highest energy point in pathways leading to the products. The
relative energies of TS1a and TS1b indicate that in the case of
TpBr3Ag, N2C(Ph)CO2Et will react before that N2C(H)CO2Et. We
analyze the origin of the discrimination on the reaction of the
first diazo molecule with the metal complex through ONIOM-
(B3LYP : MM3) calculations with a mechanical embedding
scheme (see Fig. S2, ESI†). This proved that the reason is purely
electronic, when using an MM description for phenyl the dis-
crimination disappeared.
Starting from the favoured metallocarbene (8a), two close
energy competing pathways lead to cross-coupling product (3)
and azine (4), through transition states with relative free ener-
gies of 11.8 kcal mol−1 (TS2CC) and 12.3 kcal mol−1 (TSAZ),
respectively. Further, these two transition states yield the 3 : 4
ratio of 70 : 30, which is in reasonable agreement with the
experimental value (90 : 10). The most stable transition states
leading to the E and Z forms of the cross-coupling products
hold the barrier heights of 11.8 and 11.9 kcal mol−1, giving
rise to the computed E : Z ratio of 54 : 46, which is in agree-
ment with the experimentally observed value (58 : 42). In both
transition states, Ag–C and C–N bonds are in the antiperi-
planar conformation (Scheme 3). The favourable cross-coupling
product, 3 (E), is −81.1 kcal mol−1 below the entry channel
Computational studies
The proposed mechanism for the reaction of N2C(Ph)CO2Et
(6a) and N2C(H)CO2Et (6b) catalyzed by TpxM (5) is shown
in Scheme 3. The first step of this mechanism is the coordi-
nation of 6a and 6b to the catalyst (5). Starting from the result-
ing complexes (7a and 7b), N2 dissociation leads to the active
metallocarbene intermediates 8a and 8b via TS1a and TS1b,
respectively. These metallocarbenes can react with N2C(Ph)-
CO2Et (6a) or N2C(H)CO2Et (6b) to form the cross-coupling
(CC) product (3), homocoupling (HC) products (1 and 2), and
azine (AZ, 4) (see Fig. S1a, ESI†). The cross-coupling and
homocoupling processes undergo through TS2. It is well-
known from the literature12 that TS2 should have an antiperi-
planar arrangement of the M–C and C–N bonds, but this
leaves still some conformational flexibility associated with the
approach of the two fragments. We report here only the most
stable conformation of TS2, information on the conformation-
al search can be found in the ESI† section.
TpBr3M systems
First, we computed the free energy profiles for the reaction
of N2C(Ph)CO2Et (6a) and N2C(H)CO2Et (6b) catalyzed by
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Scheme 4 Free energy profiles (kcal mol−1) for the reaction of N2C(Ph)CO2Et (6a) and N2C(H)CO2Et (6b) catalyzed by (A) TpBr3Ag and (B) TpBr3Cu.
(not shown in the free energy profile). The alternative pathway
leading to the homocoupling product (2) from 8a must be dis-
carded because of the high barrier of the transition state
(22.9 kcal mol−1 for TS2HC, more than 10 kcal mol−1 than the
competing pathways). Therefore, there is a strong preference
for N2C(H)CO2Et to be the second substrate to react with the
system. We attribute this preference to steric effects, as the
system becomes too crowded to accept a second substrate con-
taining a phenyl group.
For the sake of completion, we also checked the barriers for
the homocoupling and cross-coupling starting from the less
favourable metallocarbene, 8b, red lines in Scheme 4A. The
free energies for the corresponding transition states are prohi-
bitively high 21.5 kcal mol−1 (TSHC′) and 23.2 kcal mol−1
(TSCC′) to compete with the pathways through 8a. It is however
Fig. 1 Optimised structures of 7a: (A) Ag-based system and (B) Cu-based
system.
IPrMCl systems
worth remarking that the entry of 6a as a second substrate According to the experimental observations, IPrCuCl and
molecule, leading in this case to homocoupling, is also IPrAgCl systems cannot perform cross-coupling of N2C(Ph)-
favoured.
CO2Et and N2C(H)CO2Et, and they only become active in the
Calculated free energy profiles for the analogous TpBr3Cu presence of a base, NaBAr4′ . This observation and previous
system are shown in Scheme 4B. The most striking difference reports in the literature11 suggested that NaBAr4′ could abstract
is that now the formation of 8b has a lower free energy barrier Cl− from IPrMCl, leading the active precursors, IPrM+ that may
(19.5 kcal mol−1) than that of 8a (22.6 kcal mol−1). This is due initiate the catalytic cycle. However, the Au-based system is not
to the fact that the coordination of N2C(Ph)CO2Et to the active for cross-coupling or homocoupling. We carried out DFT
TpBr3Cu is difficult, as the Cu-coordination sphere (i.e., Cu– calculations to understand these puzzling observations.
ligand bond distances) is relatively smaller than the Ag-based
Our calculations (summarized in Scheme 5) indicated that
system (Fig. 1). As a result, computed free energies of 7a and it is more difficult to form the IPrM+ active species from the
the subsequent transition state for the N2 dissociation are rela- starting IPrMCl + NaBPh4 in the case of gold. The relative ener-
tively higher in energy. Therefore, 8b is the active metallo- gies are 19.5 kcal mol−l for the copper system, 21.9 kcal mol−l
carbene intermediate in solution. Starting from 8b, binding of for the silver system, and 28.0 kcal mol−l for the gold system.
N2C(H)CO2Et as the second diazo molecule is favored due to As a result, the availability of IPrAu+ will be lower than that of
steric reasons, analogously to the silver system. However, in IPrCu+ and IPrAg+, which explains the inferior reactivity of the
this case binding of a second unit of 6b leads to the homo- gold system. This is not in contradiction with the efficiency of
coupling product.
the IPrAuCl + EDA system for other processes such as C–H
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activation,11 because the reactivity depends both on concen- 99 : 1 reproduced the experimental trend (E : Z = 80 : 20).
tration and energy barrier.13
Similar features can be seen for the analogous Cu-based
Our experimental results showed that both the IPrCu+ and system, where the calculated barriers for the E (17.8 kcal mol−1
)
IPrAg+ systems prefer cross-coupling rather than homo- and Z (20.4 kcal mol−1) products yield the E : Z ratio of 99 : 1,
coupling. According to the free energy profiles (Scheme 6), N2 which also supports the experimental observations (76 : 24).
dissociation from N2C(Ph)CO2Et bound complex (7a) is easier
We observed azine as a side product with both the
than the N2C(H)CO2Et bound species (7b) in both systems. catalysts, and our calculated 3 : 4 ratio of 99 : 1 for the Ag-
Therefore, the reaction passes through the metallocarbene 8a, based system and 100 : 0 for the Cu-based system support
leading to the desired cross-coupling product, 3. In the case of the experimental trends. It is important to note that the
IPrAg+, E and Z forms of 3 are formed with barriers of 15.5 and IPrCu+ system provides homocoupling product (2) as
a
18.2 kcal mol−1, respectively. Further, the calculated E : Z ratio of minor product due to the fact that the energy separation
between TS1a and TS1b is only 2.6 kcal mol−1, and therefore
the metallocarbene 8b can be formed. However, we did
not observe homocoupling product (1) in the case of
IPrAg+, because the energy gap between TS1a and TS1b is
5.5 kcal mol−1
.
Our calculations reproduce all experimental observations,
and provides a simple rationalization for them. Computational
chemistry is thus a promising tool for the evaluation of the
potential efficiency of new ligands for this chemical process
prior to their experimental testing.
Conclusions
We have shown that TpxAg and IPrMCl + NaBAr′4 (M = Cu and
Ag) complexes are active catalysts for the cross-coupling reac-
tion of N2CHCO2Et and N2C(Ph)CO2Et to afford heterocoupled
olefins EtO2C(H)CvC(Ph)CO2Et, which constitute the first
example of group 11 metal-based catalysts at this level of
efficiency. The related TpxCu complexes exclusively lead to the
Scheme 5 Free energy profiles (kcal mol−1) for the formation of IPrM+ from
IPrMCl.
Scheme 6 Free energy profiles (kcal mol−1) for the reaction of N2C(Ph)CO2Et and N2C(H)CO2Et catalyzed by (A) IPrAg+ and (B) IPrCu+.
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homocoupling products, EtO2C(H)CvC(H)CO2Et. IPrAuCl that the stationary points were minima or transition states. All
does not react under similar conditions. transition states had a single imaginary frequency in the
This diverse reactivity could be explained by a compu- optimization in solvent phase. Free energy corrections at
tational study on the reaction mechanism. The reaction takes 298.15 K and 105 Pa pressure were used, including zero point
place in a mononuclear complex, with one diazo compound energy corrections. Connectivity of the transition state struc-
reacting sequentially after the other. In all reacting systems tures was confirmed by relaxing the transition state geometry
except TpxCu, the initial reaction with N2C(Ph)CO2Et is favored towards both the reactant and the product. Single-point test
because of electronic reasons.
The second diazo compound to react is always N2C(H)- agreement with experiment than the B3LYP calculations, there
CO2Et due to steric reasons. As result, the hetero- seems to be some problem with the introduction of dispersion
coupling product is obtained from TpxAg and IPrMCl (M = Cu corrections in these systems.
calculations with M06 and B97D produced slightly worse
a
and Ag), and the homocoupling product from TpxCu. The lack
Hybrid
quantum
mechanics/molecular
mechanics
of reactivity of IPrAuCl is satisfactorily explained by the higher (QM : MM)24 calculations were performed with a new ONIOM-
energy cost of displacement of the Cl− group to produce the (DFT : MM3) implementation developed by our group, where
active catalyst.
we used the Gaussian09 standardized interface to run
Tinker6.0.25
Experimental section
General manipulations
Acknowledgements
All experiments were performed using conventional vacuum
line and Schlenk techniques or in a drybox. The complexes
TpxM14 and IPrMCl15 were prepared according to literature
procedures as well as the diazo compounds ethyl-2-diazo-
acetate-2-phenylacetate16 and NaBAr′4 (Ar′ = tetrakis(3,5-bis-
(trifluoromethyl)phenyl)borate).17 Ethyl diazoacetate was pur-
chased from Sigma Aldrich. NMR spectra were recorded at
298 K using a Varian Mercury 400 instrument. GC were run in
a Varian 3900 model.
We thank MINECO (CTQ2011-28942-CO2-01, CTQ2011-27033
and Consolider Ingenio 2010 CSD2006-0003), Junta de
Andalucía (Proyecto P10-FQM-06292), Generalitat de Catalunya
(2009SGR-2059 and Xarxa de Referència en Química Teòrica i
Computacional) and the ICIQ Foundation for financial
support.
Notes and references
General catalytic reaction
In a typical experiment, the catalyst (0.0125 mmol) was dis-
solved in 5 mL of the CH2Cl2. In the case of IPrMCl complexes,
1 equiv. of NaBAr4′ was added to the above solution. Then,
ethyl-2-diazoacetate (0.25 mmol) and ethyl-2-diazoacetate-
2-phenylacetate (0.25 mmol) were added in one portion. The
reaction mixture was stirred at 5 °C until no diazo reagents
were detected by GC. The volatiles were removed under
vacuum, and the residue was purified by SiO2-column
chromatography with AcOEt–petroleum ether (10 : 1). NMR
studies revealed the formation of three products (see eqn (2)).
The compounds were identified by comparing with the litera-
ture data.10,18
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Computational details
All calculations were performed using DFT with the B3LYP
functional as implemented in the Gaussian09 program.19 The
LanL2DZ20 basis set and associated effective core potentials
with a single f polarization function were used for Ag (1.611),
Cu (3.525), and a d polarization was added for Br (0.4280).21
The 6-31G(d) basis set was used for the C, H, N, O, and B
atoms.22 The SMD approach of Truhlar and co-workers was
applied for solvation treatments,23 where dichloromethane (ε =
8.93) was used as the solvent. All structure optimizations were
full in the solvent phase with no restrictions, and vibrational
frequency calculations were performed in order to confirm
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S. Sakaguchi and Y. Ishii, Chem. Commun., 2000, 625–626;
(b) H. Bock and H. P. Wolf, J. Chem. Soc., Chem. Commun.,
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