A Noble-Metal-Free Metal–Organic Framework (MOF) Catalyst for the Highly Efficient Conversion of CO2 with Propargylic Alcohols

Article abstract of DOI:10.1002/anie.201811506

Cyclization of propargylic alcohols with CO₂ is an important reaction in industry, and noble-metal catalysts are often employed to ensure the high product yields under environmentally friendly conditions. Herein a porous noble-metal-free framework 1 with large 1D channels of 1.66 nm diameter was synthesized for this reaction. Compound 1 exhibits excellent acid/base stability, and is even stable in corrosive triethylamine for one month. Catalytic studies indicate that 1 is an effective catalyst for the cyclization of propargylic alcohols and CO₂ without any solvents under mild conditions, and the turnover number (TON) can reach to a record value of 14 400. Furthermore, this MOF catalyst also has rarely seen catalytic activity when the biological macromolecule ethisterone was used as a substrate. Mechanistic studies reveal that the synergistic catalytic effect between Cu^I and In^III plays a key role in the conversion of CO₂.

Full text of DOI:10.1002/anie.201811506

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Accepted Article
Title: Noble-Metal-Free MOFs Catalyst Exhibiting High Efficient
Conversion of CO2 with Propargylic Alcohols
Authors: Bin Zhao, Sheng-Li Hou, Jie Dong, Xiao-Lei Jiang, and Zhuo-
Hao Jiao
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Angewandte Chemie International Edition
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COMMUNICATION
Noble-Metal-Free MOFs Catalyst Exhibiting High Efficient
Conversion of CO with Propargylic Alcohols
2
Sheng-Li Hou, Jie Dong, Xiao-Lei Jiang, Zhuo-Hao Jiao, and Bin Zhao*
Abstract: Cyclization of propargylic alcohols with CO
2
is an
newly hybrid materials can be regarded as one of the most
promising and efficient catalysts for chemical transformation of
CO because of their distinctive advantages such as controllable
2
structures, tailorable functions, modifiable pores, and isolated
catalytic sites.[14] For example, Cu-based MOFs can efficiently
important reaction in industry, and noble metal catalysts are often
employed to ensure the high product yields under environmentally
friendly conditions. Herein a porous noble-metal-free framework 1
with large 1D channels of 1.66 nm diameter was rationally
synthesized for this reaction. Compound
1
exhibits excellent
catalyze cycloaddition of CO
oxazolidinones and carboxylation of terminal alkynes with CO
produce carboxylate compounds under mild conditions.[
Inspired by these works, we designed to construct stable Cu
cluster-based heterometallic MOFs to efficiently catalyze the
cyclization of propargylic alcohols with CO . In this contribution,
anionic framework
O} (1) was synthesized
by 5-aminonicotinic acid (marked as L) as the linker. Compound
1 exhibits high stability in various solvents and acid/base
solution. Catalytic results reveal that 1 can effectively catalyze
the carboxylative cyclization of various propargylic alcohols and
2
with aziridines to synthesis
acid/base stability, and even can keep stable in corrosive
triethylamine for one month. Catalytic explorations indicate that 1
can sever as an effective catalyst for cyclization of propargylic
2
to
15]
x y
I
2
alcohols and CO without any solvents under mild conditions, and
the turnover number (TON) can reach to a record value of 14400.
Furthermore, this MOF catalyst also possesses rarely catalytic
activity for biological macromolecule ethisterone. Mechanism
explorations reveal that the synergistic catalytic effect among Cu(I)
2
a
{(NH
unique
three-dimensional
·(L) ·(In)0.75]·DMF·H
2
2
C
2
H
6
)0.75[Cu
4
I
4
3
and In(III) plays key roles in the conversion of CO
is the first example that directly catalyzes cycloaddition of
propargylic alcohols with CO by noble-metal-free MOFs catalyst.
2
. Importantly, this
2
2
CO under mild conditions without any solvents, and the
turnover number (TON) can reach to 14400, which is even
higher than Ag-based homogeneous catalysts. Furthermore, due
to the large one dimensional (1D) channels in the framework,
this catalyst also works well with the biological macromolecule
ethisterone. To our knowledge, this is the first example that
noble-metal-free MOFs can directly catalyze carboxylative
As an abundant industrial exhaust gas, the growing carbon
dioxide (CO ) level in the aerosphere has become the main
responsible for global warming, and the transformation of CO
into value-added chemicals is a highly meaningful strategy with
2
2
2
the aim of both reducing CO emissions and fully utilizing cheap,
green, inexhaustible C1 source.[1] As a result, much effort has
been devoted to developing effective methods to chemical
cyclization of propargylic alcohols with CO
Block crystals of 1 were synthesized from a solvothermal
reaction of ligand L, CuI and In(NO in DMF/CH CN mixed
2
.
fixation of CO
aziridines with CO
molecules with CO
alcohols with CO
2
, mainly including the cycloaddition of epoxides or
3
)
3
3
[
2]
2
,
.
and carboxylation of terminal alkyne
solvent at 120 °C. Single crystal X-ray diffraction analysis results
indicate that compound 1 crystallizes in the tetragonal system
with I-4c2 space group (Table S1). Each asymmetric unit
consists of three ligands, a [Cu I ] cluster, and two In ions (In1
4 4
and In2) with position occupancy of 0.25 and 0.5, respectively.
Four Cu ions in the cluster are bridged by four iodide anions to
[3]
2
Recently, the cyclization of propargylic
has also aroused intense interest,[ because
4]
2
the resultant products α-alkylidene cyclic carbonates are a class
of important heterocyclic compounds in nature products
synthesis, pharmaceutical chemistry, and polymers, such as β-
ketocarboxylic
cyclopentenones,[
acids,[5]
nitropyrrolins
A−E,[6]
2-
4 4
form a tetrahedral [Cu I ] motif, and further coordinated with
7]
poly(urethane)s and poly(carbonate)s.[8]
three pyridine nitrogen atoms and one amino group (Figure 1A).
Meanwhile, there are two uncoordinated amino groups of N5
and N6 in ligands, which can be considered as potential catalytic
sites in chemical reactions. Both In1 and In2 are coordinated by
eight carboxylic oxygen atoms from ligands. The [Cu I ] clusters
4 4
and eight-coordinated In nodes in the framework are connected
by ligand L, forming a three-dimensional porous structure
However, due to the thermodynamic stability of C=O bond (bond
-
1
4
3
enthalpy +805 kJ mol ) and stable electronic structure of π
CO
in
2
, highly active catalysts are often needed in promoting this
cyclization reaction, like Ag nanoparticles, Ag salts,[10] and Ag-
MOF or nanoparticle Ag@MOFs,[11] and it should be noted that
most of these catalysts are associated with noble metal Ag.
Therefore, to reduce the cost, the explorations on efficient
catalysts with free noble metals are still highly desirable but a
great challenge.[12] To our knowledge, it has never been reported
that MOFs without noble metals can directly catalyze the
[9]
(
Figure 1B, Figure S1 and S2). XPS spectra results
demonstrated that In and Cu ions are +3 and +1 in compound 1,
respectively (Figure S3). This case implies the heterometallic
compound has an anionic framework, and the electric charge is
cyclization of propargylic alcohols with CO
2
.[13]
+
balanced by [(CH
3
)
2
NH
2
] counterions, which are generated from
Actually, our previous work has revealed that MOFs as a
[16]
in situ decomposition of DMF.
In addition, compound 1
possesses two types of 1D open channels with approximate
diameter of 1.66 nm and 0.72 nm along c direction (Figure 1C
and Figure S1), respectively. High density of [Cu I ] clusters and
4 4
uncoordinated amino groups are homogeneously dispersed in
the large nanoscopic channels (Figure 1D). Benefiting from the
porous structure, the total free volume of 1 is estimated to be
[
a]
College of Chemistry, Key Laboratory of Advanced Energy Material
Chemistry, MOE, and Collaborative Innovation Center of Chemical
Science and Engineering,
Nankai University
Tianjin 300071.
E-mail: zhaobin@nankai.edu.cn
5
2.4% as calculated by PLATON software after removal of the
guest solvent molecules.[
17]
Supporting information for this article is given via a link at the end of
the document.
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Angewandte Chemie International Edition
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COMMUNICATION
macromolecular substrate ethisterone with high steric hindrance
also can be well catalyzed to produce α-alkylene cyclic
carbonate ethisterone (2h) with the 90% yield under mild
conditions, originating from the large channels and high catalytic
activity of catalyst 1. As we known, ethisterone is the first orally
active progestin and its derivative compounds have a great
significance for pharmaceutical chemistry.[
18]
To obtain more
accurate structure information of 2h, the single crystals were
also developed after attempting various methods, and the
structure was unambiguously determined by single-crystal X-ray
diffraction analysis (Figure S9 and Table S3 to S5). To our
knowledge, it is rather rare for MOF catalysts to efficiently
catalyze such large substrates (Figure S10).[19] These results
indicate that MOF-based catalysts have a potential application in
synthesizing macromolecular drugs.
In addition, to explore the potential application in industrial
production, the catalyst efficiency for this methodology was also
evaluated in a gram-scale experiment. 16.8 g 2- methyl-3-butyn-
2
2
-ol as the substrate was reacted with CO , which is described
Figure 1. (A) The asymmetric unit in 1. Thermal ellipsoids are set at the 25%
probability level. (B) Ball−stick models of 1 along c axes. (C) The 1D large
channel in 1. Yellow cylinder indicates the channel inside the structure. (D)
in supporting information. Markedly, even after reacting six
weeks, the product is also obtained in 72% yield under mild
conditions. The corresponding TON can reach to 14400, which
[
4 4
Cu I ] clusters and uncoordinated amino groups are anchored in the
nanoscopic channels.
is even higher than that AgOAc/(n-C
7 15 4
H ) NBr catalyst (TON
6
024, Table S6).[20]
The stabilities of 1 were systematically investigated, and 1
exhibits high thermal (up to 240 °C), acid/base (pH = 2 to 12)
and solvent stability (Figure S4 to S7). Markedly, compound 1
even can keep stable in corrosive triethylamine for one month,
which is rare reported in carboxylic MOFs. Encouraged by the
excellent stability, bimetallic active center, and high density of
Table 1. Carboxylic cyclization of various propargylic alcohols. [a]
[
Cu
catalytic capacity of 1 for carboxylative cyclization of propargylic
alcohols with CO was explored. 2-Methyl-3-butyn-2-ol was
4 4
I ] clusters anchored within the nanoscopic channels, the
2
chosen as the model substrate to optimize the reaction
conditions and study the mechanism. The catalytic activities
under various conditions were investigated, and the results are
shown in Table S2. The individual catalyst 1, TEA, and other raw
materials were proved to hardly catalyze this reaction under
given conditions (Entry 1 to 9 in Table S2). It should be noted
that 1 has no catalytic activity together with aniline, but under the
existence of co-catalyst tetrabutylammonium bromide (TBAB), 1
displays considerable catalytic activity (51%). Interestingly, when
the TEA is added as additive in combination with catalyst 1, the
yield of the target product α-alkylidene cyclic carbonate can
reach to 99% (Entry 12), indicating that 1 is an excellent catalyst
2
for carboxylative cyclization of propargylic alcohols with CO to
produce α-alkylidene cyclic carbonates.
Subsquently, based on the optimized reaction conditions with
/TEA (Figure S8) system, several typical terminal propargylic
1
[
a] Reaction conditions: 20 μL TEA, 14 mg 1, 1 mmol substrate, 50 °C, 10 h, 5
alcohols with various substituents were further examined under
given conditions, and the yields of the target products are
summarized in Table 1. Terminal propargylic alcohols with
methyl, ethyl, isopropyl, tert-butyl, and phenyl substituents at the
propargylic position can afford the corresponding products α-
alkylidene cyclic carbonates (2a-2f) in high yields from 90% to
2
bar CO , solvent free except that 0.5 mL DMF was used to dissolve the
ethisterone. Yields were determined by 1H NMR with 1,1,2,2-tetrachloroethane
as the internal standard.
9
9%. In contrast, an impressive low catalytic efficiency is
Next step, several control experiments were systematically
performed to investigate the roles of Cu(I) and In(III) in this
observed in propargylic alcohol with dual reaction sites (2g),
probably due to the low activity of the reaction intermediate
propenyl alcohol in this system. More importantly, the biological
reaction (Table 2). Ligand L and In(NO
3 3
) with TEA as co-
catalyst were firstly tested, and no products were obtained
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COMMUNICATION
(
Entries 2 and 3 in Table 2), indicating that the individual L or
In(NO are ineffective for this reaction system. Meanwhile, CuI
exhibits a well performance with a yield of 48% under the same
conditions (Entry 4). In addition, after adding trace In(NO in
the CuI system, the yield of the target product can increase to
5% (Entry 6), indicative of that Cu(I) and In(III) ions exist
large channels are beneficial to transportation of substrates to
react with catalytic sites and carry products out;[24] 4) The
3 3
)
synergistic effect between Cu
TEA can effectively activate CO
reaction rate is enhanced as a result.
4
I
4
/In heterometallic framework and
3
)
3
2
to react with substrate, the
5
To explore the activation of substrates, the interactions
1
positive synergistic effect. Subsequently, high oxidation state
Cu(II) salt was also investigated, and a poor yield of 11% was
between propargylic alcohol and catalyst were monitored by H
NMR and 13C NMR (Figures S17 to S40). After adding 1 or TEA
alone (Figure 2b and c), the proton signal in hydroxyl group still
obtained by Cu(NO
than Cu(II) for this reaction. To further demonstrate these
proposed perspectives, a discrete Cu cluster coordinated by L
was rationally constructed and structurally characterized by
single-crystal X-ray diffractions (L-Cu , Figure S11 and Table
S7), and two reported MOFs HKUST-1 (Figure S12) and Cu
Gd (Figure S13) were simultaneously synthesized as
benchmark catalysts.[21,15b] As we proposed, Cu(II) based MOF
HKUST-1 exhibits low catalytic activity for carboxylic cyclization
of propargylic alcohol (Entry 7), but the corresponding yield of α-
3 2
) (Entry 5), revealing Cu(I) is more efficient
exhibits a sharp peak at δ = 5.29 ppm, which is almost
I
4
unchanged compared to the original data (Figure 2a).[
10a]
These
4
phenomena reveal that individual 1 or TEA cannot efficiently
activate the hydroxyl proton, and result in the unreacted
carboxylative cyclization. However, the proton signal becomes
broad and dwarf obviously when 1/TEA was added (Figure 2d
and Figure S21), suggesting the synergistic effect between 1
and TEA can activate the propargylic alcohol, enhance the
nucleophilicity of the hydroxyl group, and thus promote the
4 4
I
4 4
I -
3
alkylidene cyclic carbonate is higher than Cu(NO
suggests the porous structure can enhance the catalytic
performance. Besides, Cu -Gd as catalyst (Entry 8) shows a
higher yield than L-Cu (Entry 9), but 1 have better catalytic
efficiency than them under the same conditions. All results
mentioned above mean that Cu(I) ions act as the crucial
catalytic sites in 1, and In(III) ions as co-catalyst can further
enhance the cyclization reaction. Furthermore, catalyst filtration
tests clearly reveal that 1 is a heterogeneous catalyst in nature
and it is stable enough during the catalytic process (Figure S14
to S16). All these results doubtlessly suggest that catalyst 1 is
an effective catalyst with trace TEA as additive for the
3
)
2
, which
2
transformation of substrates and CO into cyclic carbonate
products (Figure S31).[25] Moreover, the signal of acetylenic
hydrogen at δ = 3.15 ppm also become broad and dwarf after
adding 1/TEA (Figure 2d), indicating that C≡C bond can be
activated by this catalyst and generated the intermediate
4
I
4
3
4 4
I
2
acetylide during reaction, which will further react with CO and
transform into products (Figure S32).[26] These results were also
confirmed by in situ IR spectra, the stretching peak of –OH in
substrate became weak and C=O peaks belong to products
gradually enhanced, revealing the activated propargylic alcohols
2
could react with CO and transform into products. (Figure S41
and S42). Based on these information, the possible mechanism
is proposed for this reaction. Initially, catalyst 1 and TEA can
synergistically activate the hydroxyl proton to form the
intermediate state (I) (Scheme S1).[27] Subsequently, the
activated oxygen atom of the hydroxyl group reacts with the
2
carboxylative cyclization of propargylic alcohols with CO . The
Table 2. Control experiments of cyclization of propargylic alcohols with CO
2
. [a]
carbon atom of CO
2
with the aid of In nodes and uncoordinated
Entry
Catalyst
Yield / % [b]
amidogens, resulting in the propargylic carbonate (II).[ In this
28]
1
1
99
<1
<1
48
11
55
16
42
64
2
step, the porous structure can enrich CO around the active sites,
which will significantly shorten the distance between catalysts
and substrates, and the reaction is accelerated as a result
2
L
3 [c]
4 [c]
5 [c]
6 [d]
7 [e]
8 [e]
3 3
In(NO )
CuI
(
Figure S43). Finally, the oxygen atom attacks the carbon atom
3 2
Cu(NO )
of terminal alkyne which has been activated by Cu(I), and ring
closure occurs with the C-O bond formation (III).[29]
Simultaneously, target products α-alkylidene cyclic carbonates
are obtained with the regeneration of the catalyst 1.[30]
3 3
CuI + In(NO )
HKUST-1
4 4
L-Cu I
9 [e]
4 4
Cu I -Gd
3
[
a] Reaction conditions: 20 μL TEA, 14 mg 1, 1 mmol substrate, 50 °C, 10 h, 5
1
bar CO
2
. [b] Determined by H NMR with 1,1,2,2-tetrachloroethane as the
internal standard. [c] 0.05 mmol Metal salts. [d] 0.05 mmol CuI and 0.01 mmol
In(NO . [e] 0.01 mmol catalysts.
3 3
)
high catalytic efficiency can be ascribed to the following aspects:
) The catalytic active sites maintain high dispersion in the
1
nanoscopic channel center (not corner) can facilitate the
interaction with TEA and substrates, and thus promote the
carboxylative cyclization;[22] 2) The porous structures can enrich
substrates and shorten the distances between substrates and
catalysts, which will promote the catalytic efficiency;[23] 3) The
6
Figure 2. Activation of the hydroxyl proton by different systems ( D -DMSO).
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Angewandte Chemie International Edition
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COMMUNICATION
In conclusion,
synthesized, and the unique structure possesses high solvent
4 4
and acid/base stabilities. The high density of accessible [Cu I ]
clusters in the nanoscopic channels can serve as efficient active
catalytic centers for carboxylative cyclization of propargylic
a
porous heterometallic framework was
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can effectively catalyze various terminal propargylic alcohols
under mild conditions, and the TON can reach to 14400.
Furthermore, the large 1D channels provide an excellent
platform for transformation of biological macromolecule, and
cycloaddition of ethisterone is successfully performed in this
catalyst system. Mechanism explortaions uncover that in 1 Cu(I)
ions act as the crucial catalytic sites, and In(III) ions as co-
catalyst can further enhance the cyclization reaction. Importantly,
it is the first example that free noble metal based MOFs directly
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This work was supported by the NSFC (21625103, 21571107,
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Angewandte Chemie International Edition
10.1002/anie.201811506
COMMUNICATION
Table of Contents
A porous anionic framework 1 was
Sheng-Li Hou, Jie Dong, Xiao-Lei
rationally designed to catalyze
Jiang, Zhuo-Hao Jiao, and Bin Zhao*
carboxylative
cyclization
of
propargylic alcohols with CO
2
, and
Page No. – Page No.
the TON can reach to a record value
of 14400 under mild conditions. 1
represents the first example that
noble-metal-free MOFs can directly
catalyze carboxylative cyclization of
Noble-Metal-Free MOFs Catalyst
Exhibiting High Efficient
2
Conversion of CO with Propargylic
Alcohols
2
propargylic alcohols with CO .
This article is protected by copyright. All rights reserved.