Assessing the bronsted basicity of diaminoboryl anions: Reactivity toward methylated benzenes and dihydrogen

Article abstract of DOI:10.1002/anie.201402175

Treatment of toluene or p-xylene with diaminoboryllithium results in consecutive reactions, involving boryl-anion-mediated deprotonation at the benzylic position followed by nucleophilic substitution at the boron center, producing benzylborane species and

Full text of DOI:10.1002/anie.201402175

Angewandte
Chemie
DOI: 10.1002/anie.201402175
Super Bases
Assessing the Brønsted Basicity of Diaminoboryl Anions: Reactivity
toward Methylated Benzenes and Dihydrogen**
Nicole Dettenrieder, Yoshitaka Aramaki, Benjamin M. Wolf, Cꢀcilia Maichle-Mçssmer,
Xiaoxi Zhao, Makoto Yamashita,* Kyoko Nozaki,* and Reiner Anwander*
Abstract: Treatment of toluene or p-xylene with diaminobor-
yllithium results in consecutive reactions, involving boryl-
anion-mediated deprotonation at the benzylic position fol-
lowed by nucleophilic substitution at the boron center,
producing benzylborane species and LiH. Diaminoboryl-
lithium also cleaves H2 heterolytically affording diaminohy-
droborane and LiH, while the reaction of lithium
diaminoboryl(bromo)cuprate with H2 takes place accompa-
nied by reduction of CuI to give diaminohydroborane, LiH,
and Cu0.
hydridoborate d. More recently, Bertrand et al. reported that
the B–H moiety in CAAC (cyclic (alkyl)(amino)carbene)
coordinated dicyanoborane could be deprotonated by treat-
ment with KN(SiMe3)2 in the presence of dibenzo-18-crown-6
to form the corresponding boryl anion [(CAAC)B(CN)2]À.[2d]
This finding indicated that the basicity of the donor-stabilized
boryl anion [(CAAC)B(CN)2]À is lower than that of
KN(SiMe3)2 [pKa of HN(SiMe3)2: 25.8].[5] Herein, we provide
clear evidence for the deprotonation of benzylic methyl
groups by 1a, implying that the basicity of À[B(NDipCH)2] is
À
higher than that of H2CPh (pKa of toluene: 40–43),[6] which
S
ince the isolation of boryllithium (THF)2Li[B(NDipCH)2]
means that the pKb of À[B(NDipCH)2] must be lower than
À26. Deprotonation of the dihydrogen molecule (pKa ꢀ 35)[6]
was also examined to clarify the nature of the boryl anion as
a Brønsted base.
(1a, Dip = 2,6-iPr2C6H3),[1] the nucleophilicity of the boryl
anion has been thoroughly studied by employing various
organic and inorganic electrophiles.[1,2] Although carbanions
have been extensively utilized as Brønsted bases, little
attention has been paid to the basicity of boryl anions.[3]
One of the few examples shows that treatment of
Br[B(NtBuCH)2] with Na/K alloy and 15-crown-5 in toluene
generates PhCH2[B(NtBuCH)2] and H[B(NtBuCH)2].[4] The
boron-bonded hydrogen atom in product H[B(NtBuCH)2]
was proven to originate from toluene by use of [D8]toluene.
Two possible mechanisms were proposed for the formation of
The reaction of isolated boryllithium 1a with toluene
afforded the benzylborane species PhCH2[B(NDipCH)2] (2,
Scheme 2).[7] When 1a was treated with 1.6 equiv of toluene
at ambient temperature in a [D12]cyclohexane solution, an
almost complete conversion of 1a into 2 was observed after
four days. In addition to 2, the formation of a small amount of
a white precipitate was detected. In contrast, the reaction of
p-xylene with 2 equiv of 1a in [D12]cyclohexane afforded
mono- (4) and disubstituted products (5), accompanied by the
formation of H[B(NDipCH)2] (3a) and again a white precip-
itate. Analysis of the resulting white solid by diffuse
reflectance FTIR spectroscopy indicated the presence of
LiH. Formation of 4 could not be suppressed by either
applying 3 equiv of 1a or by changing the solvent to [D8]THF.
Products 4 and 5 could be isolated from a reaction in n-hexane
as crystalline solids in yields of 19 and 15%, respectively,
suitable for X-ray crystallographic analyses (Figure 1 and
Figure S37; Supporting Information).[8]
À
the B H bond, namely either proton abstraction by a boryl
anion or hydrogen radical abstraction by a boryl radical.
Radical coupling would also induce the formation of the
À
benzyl B bond in PhCH2[B(NtBuCH)2]. Later on, targeting
putative Li[B(NMesCH2)2] (Mes = 2,4,6-Me3C6H2) as a struc-
tural modification of seminal boryllithium 1a[1] led to the
intramolecular cyclization product e (Scheme 1).[2h] Of the
two possible reaction mechanisms, radical versus ionic, the
anionic pathway shown in Scheme 1 seemed more likely
based on the clean conversion of boryllithium b into cyclic
[*] N. Dettenrieder, B. M. Wolf, Dr. C. Maichle-Mçssmer,
Prof. Dr. R. Anwander
by the German Science Foundation (grant no. AN 238/14-2), the
Funding Program for Next Generation World-Leading Researchers,
Green Innovation (for K.N.), and Grants-in-Aid for Scientific
Research for Innovative Areas [“Stimulus-Responsive Chemical
Species for Creation of Fundamental Molecules” (24109012 for
M.Y.)] from MEXT. We are grateful to Dr. Y. Ogasawara, Prof. K.
Yamaguchi, and Prof. N. Mizuno (The University of Tokyo) for XPS
analysis. Y.A. is grateful to the Japan Society for the Promotion of
Science (JSPS) for a Research Fellowship for Young Scientists. X.Z.
is grateful to the Global COE Program “Chemistry and Innovation
through Cooperation of Science and Engineering” from JSPS. The
computations were performed at the Research Center for Compu-
tational Science, Okazaki (Japan).
Institut fꢀr Anorganische Chemie
Eberhard Karls Universitꢁt Tꢀbingen
Auf der Morgenstelle 18, 72076 Tꢀbingen (Germany)
E-mail: reiner.anwander@uni-tuebingen.de
Dr. Y. Aramaki, Dr. X. Zhao, Prof. Dr. K. Nozaki
Department of Chemistry and Biotechnology
Graduate School of Engineering, The University of Tokyo
7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8657 (Japan)
Prof. Dr. M. Yamashita
Department of Applied Chemistry
Faculty of Science and Engineering, Chuo University
1-13-27 Kasuga, Bunkyo-ku, Tokyo 112-8551 (Japan)
Supporting information for this article is available on the WWW
under http://dx.doi.org/10.1002/anie.201402175.
[**] K.N. and R.A. are grateful to the University of Tꢀbingen and BASF for
supporting the Schlenk Lecture program. This work was supported
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Scheme 1. Two previously proposed reaction mechanisms for the formation of cyclic diaminoalkylborane e by the reduction of bromoborane a.
Scheme 3. Proposed mechanism for the formation of benzylborane 2
and LiH from 1a and toluene. Bn=benzyl.
Scheme 1.[2h] Since the incorporation of deuterium into the
products was not observed in [D8]THF, this solvent can be
excluded as a proton source. Hence, boryllithium initially
deprotonates the methyl group of toluene to give 3a and
Scheme 2. The reaction of boryllithium 1a with toluene and p-xylene.
benzyllithium. Next, a nucleophilic attack of the anionic
benzyl carbon at the boron center leads to the formation of
hydridoborate intermediate 6. Subsequent elimination of
hydride affords benzylborane 2 and LiH precipitation. Since
the reaction started from isolated boryllithium, and not by
reduction of borylbromide, a radical pathway is unlikely due
to the polarity of the B–Li bond. The ionic reaction
mechanism, involving boryllithium as a strong base, was
corroborated by the formation of 2 (via 6) from the reaction
of hydroborane 3a with benzyllithium as monitored by
1H NMR spectroscopy.[9]
The deprotonation capability of boryllithium could be
further proven by the heterolytic cleavage of dihydrogen.
Figure 1. ORTEP view of compound 5. The atomic displacement
Exposure
of
a
[D6]benzene
solution
of
parameters are set at the 50% probability level, hydrogen atoms are
omitted for clarity, and the carbon atoms of the aromatic parts are
shown with reduced radii. Selected bond lengths [ꢂ] and angles [8]:
B1–C1 1.578(2), C1–C101 1.516(2); B1-C1-C101 115.97(9).
(THF)2Li[B(NDipCH2)2] (1b) to H2 for 10 min produced
1
a fine-grained white precipitate (LiH), while the H NMR
spectrum indicated complete conversion of 1b into hydro-
borane 3b (Scheme 4, top). This result clearly indicated that
À
boryllithium 1b splits the H H bond heterolytically. The
reaction of 1b with D2 gave a broad signal at 4.3 ppm in the
Moreover, we examined the reaction of mesitylene with
3 equiv of 1a in an NMR-scale experiment (Figure S9,
Supporting Information). Heating to 458C for 20 h gave
a reaction mixture showing two peaks for the benzylic protons
in a 1:3 ratio. We tentatively assigned the major product as the
mono-activated product, (3,5-Me2C6H3)CH2[B(NDipCH)2].
The fact that mesitylene is activated at only one of the three
methyl groups can be explained by the increased steric
demand resulting from boryl units at meta-methyl groups.
With the products in hand, we propose the reaction
mechanism summarized in Scheme 3, which bears resem-
blance to the anionic pathway (top path) hypothesized in
2H NMR spectrum; this chemical shift corresponds to that of
the B–H unit of 1b in its H NMR spectrum. Addition of
1
B(C6F5)3 to the reaction mixture led to the appearance of
a small singlet at À25.1 ppm in the 11B NMR spectrum,
suggesting the presence of Li[DB(C6F5)3]. An analogous H2-
splitting reaction was also confirmed to take place with
boryllithium 1a,[1,2h] featuring an unsaturated backbone.
Similarly, when 3 equivalents of B(C6F5)3 were added to the
reaction mixture, new resonances appeared in the 11B and
19F NMR spectra, indicating the generation of Li[HB(C6F5)3]
and (THF)B(C6F5)3. As Li[HB(C6F5)3] is not completely
2
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Scheme 5. DFT-calculated relative energies for the reaction of 1b with
H2 [E: thermal energy; G: Gibbs free energy (kcalmolÀ1)]. TS:
transition state.
Scheme 4. The reaction of boryllithium 1a,b, borylmagnesium bromide
7, and lithium borylbromocuprate 8 with H2 or D2.
soluble in [D6]benzene, only about 25% of it was observed by
1H NMR spectroscopy.
This is also consistent with the fact that the reaction of 1b
with H2 is much faster than that of CAAC with H2.
In sharp contrast to the case of boryllithium 1, other
borylmetal species exhibited different reactivities with H2
(Scheme 4, middle and bottom). For example, borylmagne-
sium bromide 7[2f] did not react with dihydrogen at ambient
temperature over a period of two days, according to 1H NMR
spectroscopy. On the other hand, lithium borylbromocuprate
8[2g] gradually reacted with H2 to give hydroborane 3b over
a period of six days at ambient temperature. During the
reaction, no other signals of significant intensity besides those
Additionally, natural bond orbital (NBO) analysis was
performed to elucidate the interactions among the molecular
orbitals. The optimized transition state with NBO 143 and
NBO 102 is shown in Figure 2. In the transition state, boron,
lithium, and two hydrogen atoms form a planar, four-
membered ring with a nearly linear bond angle of B-H-H
(177.68). NBO analysis revealed that the stabilization energy
(E2) between the lone pair of the central boron atom in
À
boryllithium and a s*-orbital of H H bond was 178.64 kcal
1
of 3b and 8 were detected in the H NMR spectrum. As the
molÀ1, reflecting the shape of the NBO 143. On the other
reaction proceeded, the formation of a bronze metallic luster
was observed on the inner surface of the NMR tube. This
metallic substance was confirmed as Cu0 by XPS, most likely
originating from the decomposition of CuH at ambient
temperature.[10] Lithium borylbromocuprate 8 also reacted
with D2 and the generation of deuterated 3b was confirmed
by 1H and 2H NMR spectroscopy.
hand, E2 for the interaction between the bonding electrons in
The driving force for the reaction of boryllithium com-
pounds 1a and 1b and lithium borylbromocuprate 8 with H2
could be the lattice energy (LiH: 219 kcalmolÀ1 [11]
CuH:
;
288.6 kcalmolÀ1).[12] However, in spite of the much higher
lattice energy of MgH2 (650 kcalmolÀ1),[10] borylmagnesium
bromide 7 did not react with H2. Therefore, the lattice energy
is not the only crucial factor governing this reaction. The
higher reactivity of boryllithium 1 relative to that of
borylmagnesium bromide 7 can be rationalized on the basis
of the enhanced reactivity of organolithium compared to that
of the respective Grignard reagents. In the case of borylcup-
rate, dihydrogen would undergo oxidative addition to form
labile (boryl)CuIIIH2 species, which undergo reductive elim-
ination to hydroborane and CuH.
In order to elucidate the mechanism of the reaction of 1b
with dihydrogen, DFT calculations were performed using the
B3LYP[13] method and 6-311G(d,p) as a basis set and the
polarizable continuum model (PCM)[14] (solvent: benzene).
The Gibbs free energy of activation was calculated as DG° =
19.9 kcalmolÀ1 (Scheme 5), which is consistent with the
experimental observation that the reaction of 1b with H2
proceeded at ambient temperature. It is noteworthy that the
value DG° = 19.9 kcalmolÀ1 is lower than that of cyclic
alkyl(amino)carbene (CAAC) with H2 (23.6 kcalmolÀ1).[15]
Figure 2. Optimized transition state for the reaction of 1b with H2
determined by using NBO analysis (isovalue=0.02); the NBO 143
(top) and NBO 102 molecular orbitals (bottom) describe the donor–
acceptor interactions. (Dip groups are shown as wire-frame models for
clarity).
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molecular orbital.[16]
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À
À
H H bond to vacant orbitals on the Li cation.
In conclusion, the reactivity of boryllithium as a Brønsted
base has been demonstrated. The deprotonation of benzylic
methyl groups by Li[B(NDipCH)2] has been clearly proven,
suggesting that the pKb of À[B(NDipCH)2] must be lower than
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¯
[8] Compound 4 (C34H45BN2, Mr = 492.53): R3, a = 41.0460(6), b =
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c = 9.3554(1) ꢃ,
V= 13650.1(3) ꢃ3,
dcalcd =
1.078 gcmÀ3, Z = 18, wR2 = 0.1182, R1 = 0.0453. Compound 5
(C60H80B2N4, Mr= 878.90): Pbca, a = 9.9970(4), b = 20.1712(8),
c = 27.029(2) ꢃ, V= 5450.4(4) ꢃ3,
d , Z = 4,
calcd = 1.071 gcmÀ3
wR2 = 0.1045, R1 = 0.0410. CCDC 982036 (4) and 982037 (5)
contain the supplementary crystallographic data for this paper.
These data can be obtained free of charge from The Cambridge
Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_
request/cif.
Received: February 7, 2014
Published online: && &&, &&&&
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Keywords: boryllithium · basicity · diaminoboryl anions ·
.
hydrogen · methylated benzenes
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Super Bases
N. Dettenrieder, Y. Aramaki, B. M. Wolf,
C. Maichle-Mçssmer, X. Zhao,
M. Yamashita,* K. Nozaki,*
R. Anwander*
&&&& — &&&&
Back to basics: The deprotonation reac-
tions of methylated benzenes and H2 by
superbasic boryl anions were studied. In
the reaction of methylated benzenes,
subsequent nucleophilic substitution on
the boron center of intermediate B–H
produces benzylborane species (struc-
Assessing the Brønsted Basicity of
Diaminoboryl Anions: Reactivity toward
Methylated Benzenes and Dihydrogen
ture of the B unit shown in the scheme;
Dip=2,6-iPr2C6H3). A general mecha-
nism for these reactions is elaborated and
the reactivity of B-Li(THF)2 toward H2
investigated by DFT calculations.
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