Metal-free Carbon Monoxide (CO) Capture and Utilization: Formylation of Amines

Article abstract of DOI:10.1002/adsc.201900185

The capture and utilization of CO by 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) were performed in the absence of transition-metal complexes. The reaction of TBD with CO afforded TBD-CO adducts, which were converted to formylated TBD (TBD-CHO). TBD-CO adducts may include an interaction of CO with positively charged species based on NMR and IR analysis. In the presence of amines, CO was transferred from TBD-CO to amines, producing formylated amines with good yields. The reaction mechanism involving TBD-CO adducts is presented based on theoretical calculations. (Figure presented.).

Full text of DOI:10.1002/adsc.201900185

Title: Metal-free Carbon Monoxide (CO) Capture and Utilization:
Formylation of Amines
Authors: Hyeong-Wan Noh, Youngjoon An, Seulchan Lee, Jaehoon
Jung, Seung Uk Son, and Hye-Young Jang
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To be cited as: Adv. Synth. Catal. 10.1002/adsc.201900185
Link to VoR: http://dx.doi.org/10.1002/adsc.201900185

Advanced Synthesis & Catalysis
10.1002/adsc.201900185
Very Important Publication
COMMUNICATION
DOI: 10.1002/adsc.201((will be filled in by the editorial staff))
Metal-free Carbon Monoxide (CO) Capture and Utilization:
Formylation of Amines
a
b
a
b
c
Hyeong-Wan Noh, Youngjoon An, Seulchan Lee, Jaehoon Jung, * Seung Uk Son,
a
Hye-Young Jang *
a
Department of Energy Systems Research, Ajou University, Suwon 16499, South Korea
Tel: +82-31-219-2555, Fax: +82-31-219-1615, E-mail: hyjang2@ajou.ac.kr
Department of Chemistry, University of Ulsan, Ulsan 44610, South Korea
b
E-mail: jjung2015@ulsan.ac.kr
Department of Chemistry, Sungkyunkwan Universiy, Suwon 16419, South Korea
c
Received: ((will be filled in by the editorial staff))
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201######.
Abstract. The capture and utilization of CO by 1,5,7- metal-free chemical conversion of CO
2
to various
[11]
triazabicyclo[4.4.0]dec-5-ene (TBD) were performed in the carbonyl compounds.
However, TBD-CO adduct
absence of transition-metal complexes. The reaction of formation or the reaction of CO with TBD in the
TBD with CO afforded TBD-CO adducts, which were absence of metal species has not been reported. The
converted to formylated TBD (TBD-CHO). TBD-CO development of a novel method for CO activation by
adducts may include an interaction of CO with positively
charged species based on NMR and IR analysis. In the
presence of amines, CO was transferred from TBD-CO to
amines, producing formylated amines with good yields.
The reaction mechanism involving TBD-CO adducts is
presented based on theoretical calculations.
TBD would allow CO capture and utilization without
transition metal complexes.
Here, we report the formation of a novel organic
CO fixation material (a TBD-CO adduct), in which
CO is captured in the dimeric TBD structure.
Although studies of capturing CO in superacids (HF-
SbF
5
or HSO
3
F-SbF ) have been conducted, CO
5
Keywords: CO capture; CO utilization; metal-free; TBD;
formylation
[12]
fixation in basic media has not been evaluated.
TBD-CO adducts were converted to TBD-CHO,
which transferred a formyl group to a variety of
[13]
amines with good yields. Considering the utility of
formylated amines in various organic syntheses, the
C-N bond formation of amines using a C1 source is a
Transition metal-catalyzed direct carbonylation
using carbon monoxide (CO) has been conducted in a
wide range of synthetic, pharmaceutical, industrial,
and biological processes.[ The advantages of CO,
e.g., cost-effectiveness and easy accessibility, have
encouraged chemical industries to develop CO-based
chemical processes such as Fischer-Tropsch process,
[14,15]
1-3]
valuable synthetic method.
The optimal reaction
conditions and substrate scopes of amine formylation
were determined using 1) pressurized CO with TBD
and 2) TBD-CO adducts. Synthesis, analysis, and
mechanistic results related to TBD-CO adducts are
presented with theoretical calculations.
hydroformylation, and acetic acid synthesis
processes.[
1,2,4]
In contrast to the extensive studies of
The reaction of TBD with CO (30 bar) afforded
TBD-CHO with 21% yield after purification by silica
column chromatography (Scheme 2). Interestingly,
the crude mixture of the reaction of TBD and CO had
different NMR and IR spectra compared with the
spectra of TBD-CHO (Figures 1 and 2 and supporting
metal-involved CO utilization, metal-free CO
reactions are rarely reported, because CO does not
[5]
have high reactivity with organic compounds.
There are only a few CO reactions without metal
complexes; e.g., carbene-mediated ketene
formation, and boron-mediated reactions with CO
[6]
1
Scheme 1).[ Considering the synthetic utility and
7]
information). The H NMR spectrum of a crude
(
mixture of TBD-CO adducts (major) and TBD-CHO
sustainability issue of CO as a C1 source, the metal-
free fixation and utilization of CO would provide
useful and environmentally benign protocols for
various carbonylation processes.
(
minor) had a major peak at 9.52 ppm, presumed to
be a proton interacting with CO in TBD-CO adducts,
and peaks at 2.85, 2.24, and 1.19 ppm corresponding
to aliphatic protons of the TBD framework (Figure
1
,5,7-Triazabicyclo[4.4.0]dec-5-ene (TBD) is a
1
3
1
b). In the CNMR spectrum of this mixture, a peak
well-known nucleophilic guanidine base, which is
at 161 ppm corresponding to a carbon of TBD-CO
used in various organic reactions, e.g., esterification,
[16]
[8-10]
adducts was observed (Figure 1d). Based on the
integration values, this compound may be composed
of two TBD molecules and one CO molecule
amidation, aldol reaction, and CO
known that reactive TBD-CO zwitterions form in
CO fixation; these are key intermediates for the
2
fixation.
It is
2
2
1
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Advanced Synthesis & Catalysis
10.1002/adsc.201900185
1
(
supporting information). The H NMR spectrum of
TBD-CHO showed a formyl group at 8.14 ppm and
six different CH groups at 3.25, 3.10, 2.60, 2.32,
.30, and 1.09 ppm (Figure 1c). Accordingly, the
mixture of TBD-CO adducts (major) and TBD-CHO
(minor) and (e) TBD-CHO in benzene-d .
6
2
1
formyl group was attached to one of the nitrogen
atoms of TBD.
The IR spectrum of TBD-CO adducts revealed a
-1
peak at 2279 cm , which was higher than that of free
-1
CO (2143 cm ) (Figure 2b). According to a previous
[12a]
study of the IR frequency of cationic CO,
the
bond strength of protonated CO is stronger compared
to that of free CO. Based on IR and NMR analysis,
we believe that TBD adducts involve the partial
protonation or interaction of CO molecules with a
positively charged species in the dimeric TBD
[13]
structure (Scheme 2).
In contrast to TBD-CHO,
TBD-CO adducts liberated CO at an ambient pressure,
which demonstrated the non-covalent interaction of
CO with TBD (see supporting information, Scheme
S1). In addition, theoretical calculations were
performed to confirm the formation of this
intermediate. The reaction conditions for TBD-CO
adduct formation were optimized, which included the
pressure of CO, reaction temperature, and reaction
time (supporting information Figure 1S-3S). TBD-
CO adducts were formed with the best conversion
when 30 bar of CO was applied at 100 C for 18 h.
(a)
Scheme 1. Metal-free CO fixation.
(
b)
c)
(
Scheme 2. Formation of TBD-CHO via TBD-CO adducts.
(a)
Figure 2. IR spectra of (a) TBD, (b) TBD-CO adducts, and
(
c) TBD-CHO.
(b)
Next, we performed TBD-mediated CO fixation
for amine formylation. The TBD-mediated direct
formylation of amines using CO was investigated
using 4-methoxy benzyl amine, as shown in Table 1.
First, pressurized CO with TBD was used, assuming
that TBD-CO adducts were formed in situ. TBD (0.5
equiv) was used in toluene at 100 C under 30 bar of
CO to form formylated product 1 with 33% yield
(c)
(
d)
(e)
(
entry 1). By increasing TBD to 1.5 equiv, the yield
of 1 was increased to 90% (entries 2 and 3).
Following the reduction of CO pressure to 20 bar, the
yield was decreased to 64% (entry 4). The analogous
organic bases, methyl-substituted TBD (MeTBD) and
1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) were
ineffective, indicating that guanidine bases with an
1
Figure 1. H NMR spectra of (a) TBD, (b) a mixture of
TBD-CO adducts (major) and TBD-CHO (minor), and (c)
TBD-CHO in benzene-d
1
3
6
,
C NMR spectra of (d) a
2
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Advanced Synthesis & Catalysis
10.1002/adsc.201900185
N-H group are essential for this reaction (entries 5
groups, were used and the selective formylation of
amines occurred in the generation of formyl amines
8-12 with good yields. In the case of N-phenylethane-
1,2-diamine, only the formylation of the primary
amines occurred to afford 13 with 93% (CO) and
80% (TBD-CO) yields.
t
and 6). Furthermore, the Inorganic base KO Bu did
not deliver the desired product (entry 7). In addition
to toluene, CH
used. The reaction in CH
yields, and no product was observed in DCE (entries
and 9). Subsequent to pressurized CO reactions,
3
CN and dichloroethane (DCE) were
3
CN afforded 1 with 28%
8
reactions with TBD-CO adducts were assessed.
Formylated amine 1 was obtained with 74% yields
with 1.5 equiv of TBD-CO, and 85% yield was
achieved with 3.0 equiv of TBD-CO (entry 10). The
stoichiometry of TBD-CO was estimated, based on
1
H NMR (supporting information). As the estimated
amounts of CO (1.5 mmol) of entry 10 were close to
1
bar of CO, 4-methoxy benzyl amine was reacted
with 1 bar of CO, affording 1 with 8% yield (entry
1
1). The yield of the reaction was slightly reduced by
an electron withdrawing group of benzyl amines; the
yields of 1 (including a methoxy group) and 1 are
9
0% and 96%, respectively, but 4-fluorobenzyl amine
was converted to 1 with 82% yield.
Table 1. Optimization of the direct formylation of
a)
benzyl amines .
Figure 3. Direct formylation of aliphatic amines.
Next, aromatic amines were subjected to
formylation under the two conditions (Figure 4).
Aniline was converted to the corresponding formyl
amine 14 (41% yield) and imine 14 (42% yield) as a
mixture under pressurized CO conditions, as well as
to 14 (27% yield) and imine 14 (28% yield) with
TBD-CO adducts. N-methyl aniline also participated
in the formylation to afford 15 with 70% (CO) and
5
8% (TBD-CO) yields. Interestingly, benzene-1,2-
a)
diamine reacted with CO followed by intramolecular
imine formation to form benzimidazole 16 with 65%
(CO) and 53% (TBD-CO) yields. Similarly,
naphthalene-1,8-diamine also formed cyclized
product 17 with 61% (CO) and 44% (TBD-CO)
yields. Unlike the diamines, the amines of 2-
aminophenol and 2-aminobenzenethiol underwent
formylation without cyclization to produce 18 and 19,
respectively.
Reaction conditions: the reaction of 4-methoxy benzyl
amine (1 mmol) and bases in the solvent (1.0 M) was
conducted at 100 C at the indicated CO pressure, TBD-
CO adducts (1.5 equiv), TBD-CO adducts (3.0 equiv)
b)
c)
To evaluate the feasibility of TBD-mediated CO
capture and utilization for amine formylation, a wide
range of aliphatic amines were examined under two
conditions: 1) 30 bar of CO with TBD and 2) TBD-
CO adducts (3.0 equiv based on CO quantity) (Figure
3
). Primary aliphatic amines (2-phenylethan-1-amine,
diphenylmethanamine, and 1-phenylethan-1-amine)
were converted to the corresponding formyl amines 2
with 98% (CO) and 87% (TBD-CO), 3 with 93%
(CO) and 80% (TBD-CO), and 4 with 95% (CO) and
82% (TBD-CO) yields. Secondary cyclic amines also
participated in the reaction to afford the desired
products 5-7 with good yields. Amines with
coordinating groups, e.g., the pyridine and hydroxyl
3
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Advanced Synthesis & Catalysis
10.1002/adsc.201900185
CO and dimeric TBD species (green iso-surface). A
high CO pressure was required in the formation of
TBD-CO adducts. The harsh reaction conditions may
be attributed to the endothermic interaction energy
between TBD and CO and their van der Waals
interaction. In particular, the enthalpy change (H)
without the effect of the entropy for the CO capture
process of dimeric TBD was H = -5.31 kcal/mol;
thus, a high pressure of CO can lead to the formation
of TBD-CO adduct by minimizing the entropy effect.
The feasibility of dimeric TBD species as a CO
capture material can also be explained by comparing
its barrier height (d3T) with that of monomeric TBD
(
Figure S1). Although the formylation of monomeric
and dimeric TBD species proceeded via
intermolecular and intramolecular hydrogen transfer,
respectively, the formylation of dimeric TBD species
was more favorable with a slightly lower barrier
height (17.41 kcal/mol) compared with that of
monomeric TBD (Figure S2 and S3). After the
formylation of TBD, the dimeric interaction was still
available through CH···N and NH···N (d4). The
hydrogen bonding, NH···N, was also important in the
interaction between benzyl amine and formylated
dimeric TBD species (d5). The barrier height of ~18
kcal/mol for the formyl group transfer from TBD to
benzyl amine was comparable to that for the
formylation of TBD, which occurred through the
geometric formation of a six-membered ring (along
red-colored bonds in the schematic structure of d6T
in Figure 5a; see also Figure S2) and resulted in the
zwitterionic intermediates (d7). Due to the instability
of zwitterionic intermediates, the C-N bond between
TBD and benzyl formamide was readily broken with
a barrier of less than 1 kcal/mol (d8T), thus
producing formylated benzyl amine and the
recovered TBD dimer. The interaction energy
between benzyl formamide and dimeric TBD species
was 7.08 kcal/mol due to three intramolecular
NH···N hydrogen bonding pairs (d9, Figure S2).
After releasing benzyl formamide, the total reaction
energy obtained with DFT calculations was –8.36
kcal/mol.
Figure 4. Direct formylation of aromatic amines.
A computational study based on the density
functional theory (DFT) was conducted to elucidate
the reaction mechanism of the metal-free formylation
of benzyl amine (a representative amine) with CO, in
which TBD was used as a CO capture material (see
supporting information for computation details). We
performed the computational procedure with
electronically neutral CO. Although spectroscopic
analysis revealed that CO molecules were partially
protonated or interacted with positively charged
species, the structure of protonated CO was not
clearly defined. Nevertheless, our computational
results indicated that TBD plays a critical role in CO
capture during formylation. Figure 5a shows the
reaction energy diagram for the formylation of benzyl
amine, in which TBD reacted with CO and
transferred the formyl group to benzyl amine. The
dimeric TBD species d1 is thought to participate in
this reaction because two TBD molecules can readily
interact with each other though hydrogen bonding,
NH···N (Figure 5b).[
13]
The interaction energy
between two TBD molecules was computationally
evaluated to be G = –5.34 kcal/mol (all energy
values hereafter are presented as G). The interaction
energy of dimeric TBD with CO was +3.94 kcal/mol,
whereas monomeric TBD interacted with CO with an
interaction energy of +4.43 kcal/mol. (see Figure S1
for the reaction energy diagram of monomeric TBD).
Despite the endothermic interaction between TBD
and CO, the large exothermic interaction energy
between two TBD molecules allowed CO binding to
the dimeric TBD to afford d2; the energy of d2 was
thermodynamically more stable than that of two
isolated TBD molecules by 1.4 kcal/mol. The
interaction characteristic between dimeric TBD
species and CO molecule was further examined by
plotting the reduced density gradient (Figure 5c) of
d2, which represents the hydrogen bonding, NH···N
In summary, we report the first case of TBD-
mediated CO capture and utilization to induce the
direct formylation of amines under metal-free
conditions. Following exposure to pressurized CO,
TBD initially formed TBD-CO adducts, which were
subsequently converted to TBD-CHO to deliver a
formyl group to amines. Experimental results,
spectral analysis, and theoretical calculations
indicated the involvement of interesting dimeric
TBD-CO adducts. The reaction mechanism of metal-
free amine formylation using TBD-CO adducts was
determined. We present a novel organic CO fixation
material that delivers CO to CO-accepting
compounds. Our TBD-CO system could be a
platform for organic carbonylation without transition
metal catalysts.
(
bond length = 1.81 Å, see Figure S2 for optimized
geometry) between two TBD molecules (blue iso-
surface), and the van der Waals interactions between
4
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Advanced Synthesis & Catalysis
10.1002/adsc.201900185
Figure 5. (a) DFT-computed reaction energy diagram (ΔG, kcal/mol) for the formylation of benzyl amine with CO, in
which the dimeric TBD species are used as a CO capture material. The chemical species along the reaction pathway are
presented using schematic structures. The detailed optimized geometries are provided in Figure S2. (b) Electrostatic
potential map for dimeric TBD species (iso-surface: 0.05 e/bohr3). Blue to red corresponds to negative to positive charge
distribution. (c) Reduced density gradient map for d2 species (iso-surface: 0.5 au). The surfaces are colored on a blue-
green-red scale according to the values of sign (λ2)ρ, ranging from –0.02 to +0.02 au. On the other hand, the blue- and
green-colored parts represent electrostatic (NH···N) and van der Waals interactions, the red part represents the steric effect
within ring structures. (O, red; N, blue; C, gray; H, white).
Experimental Section
[1] For selected review articles of carbonylation using CO,
see: a) J. N. Armor, Appl. Catal. 1991, 78, 141-173; b)
M. Beller, B. Cornils, C. D. Frohning, C. W.
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M. Tafesh, J. Weiguny, Chem. Rev. 1996, 96, 2035-
2052; d) G. Kiss, Chem. Rev. 2001, 101, 3435-3456.
Procedure for the formation of TBD-CO adducts: An
autoclave (50 ml) was charged with a solution of 1,5,7-
triazabicyclo[4.4.0]dec-5-ene (TBD) (208.8 mg, 1.5 mmol)
in toluene (1 ml). The air in the autoclave was replaced
with CO gas 10 bar with stirring. Subsequently, the
autoclave was vented, and recharged with 30 bar of CO.
The reaction mixture was stirred (500 rpm) and heated at
[2] For selected articles of CO utilizations in
pharmaceutical and industrial processes, see: a) M.
Brookhart, F. C. Rix, J. M. DeSimone, J. C. Barborak,
J. Am. Chem. Soc. 1992, 114, 5894-5895; b) D. Forster,
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Park, Y. N. Lim, S. Y. Kang, S. M. Lee, H. J. Kim, Y.-
J. Ko, B. Y. Lee, H.-Y. Jang, S. U. Son, ACS Macro
Lett. 2016, 5, 1322-1326; d) S. Y. Kang, Y. N. Lim, Y.-
J. Cheong, S. M. Lee, H. J. Kim, Y.-J. Ko, B. Y. Lee,
H.-Y. Jang, S. U. Son, Ind. Eng. Chem. Res. 2017, 56,
1
00 C for 18 h. Then, the autoclave was cooled to room
temperature, and unreacted gas was vented. The solvent
was evaporated.
General procedure for the direct carbonylation of
amines: An autoclave (50 ml) was charged with a solution
of 4-methoxy benzyl amine (137.2 mg, 1.0 mmol) and
1
,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) (208.8 mg, 1.5
mmol) in toluene (1 ml). The air in the autoclave was
replaced with CO gas 10 bar with stirring. Subsequently,
the autoclave was vented. The autoclave was recharged
with 30 bar of CO. The reaction mixture was stirred (500
rpm) and heated at 100 C for 20 h. Then, the autoclave
was cooled to room temperature, and unreacted gas was
vented. The reaction mixture was concentrated and
purified by flash column chromatography on a silica gel
1
0235-10241; Y. N. Lim, H.-W. Noh, Y.-J. Cheong, S.
Y. Kang, B. Y. Lee, S. U. Son, H.-Y. Jang, ACS
Sustainable Chem. Eng. 2017, 5, 9657-9661.
(
80 % ethyl acetate and 20% of hexane) to afford the
[3] For selected articles of carbonylation in biological
systems, see: a) T. I. Doukov, T. M. Iversion, J.
Seravalli, S. W. Ragsdale, C. L. Drennan, Science 2002,
desired product.
2
98, 567-572; b) S. W. Ragsdale, Crit. Rev. Biochem.
Acknowledgements
Mol. Biol. 2004, 39, 165-195; c) D. J. Evans, Coord.
Chem. Rev. 2005, 249, 1582-1595.
This study was supported by the C1 Gas Refinery Program (No.
2
015M3D3A1A01065436), National Research Foundation
[
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Advanced Synthesis & Catalysis
10.1002/adsc.201900185
COMMUNICATION
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Utilization: Formylation of Amines
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