Enhancing Ligand-Free Fe-Catalyzed Aminocarbonylation of Alkynes by ZrF4

Article abstract of DOI:10.1002/cctc.201900995

Zirconium fluoride was utilized to promote efficiently iron-catalyzed aminocarbonylation between alkynes and amines without the use of extra ligands. In particular, this new system is applicable to a wide range of amine and alkyne substrates affording α,β-unsaturated amides in good to excellent yields. Preliminary mechanistic studies reveal the activation model involving interactions of ZF₄ with both iron catalyst and amine substrates.

Full text of DOI:10.1002/cctc.201900995

Accepted Article
Title: Enhancing Ligand-free Fe-Catalyzed Aminocarbonylation of
Alkynes by ZrF4
Authors: Zijun Huang, Yanan Dong, Yudong Li, Mohamed Makha, and
Yuehui Li
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Enhancing Ligand-free Fe-Catalyzed Aminocarbonylation of
Alkynes by ZrF4
Zijun Huang,[a,b] Yanan Dong,[a,b] Yudong Li,[a,b] Mohamed Makha,[a] and Yuehui Li*[a]
Abstract: Zirconium fluoride was utilized to promote efficiently iron-
catalyzed aminocarbonylation between alkynes and amines without
the use of extra ligands. In particular, this new system is applicable to
a wide range of amine and alkyne substrates affording α,β-
unsaturated amides in good to excellent yields. Preliminary
mechanistic studies reveal the activation model involving interactions
of ZF4 with both iron catalyst and amine substrates.
Carbonylation represents the atom-efficient method for the
preparation of high value-added carbonyl containing
compounds.[1,2] In this regard, transition metal catalyzed
Figure 1. Selective examples of bioactive α,β-unsaturated amides
aminocarbonylation of alkynes with amines to generate α,β-
unsaturated amides has attracted broad interests in organic
synthesis.[2] This class of compounds are of importance for their
For example, ZrF4 was deployed as co-catalyst for nickel-
biological and insecticidal activities,[3] and applications in
catalyzed cross-coupling of aryl fluorides with aryl boronic
materials science.[4] For instance, α,β-cinnamamide derivatives
have medicinal uses in anti-inflammatory drugs and in the
treatment of cancer (Figure 1).[3, 5] α,β-Unsaturated amide are
figured as building blocks in natural products frameworks, too.[6]
Conventionally, α,β-unsaturated amides are prepared via
condensation reactions of amines with carboxylic acids and acyl
chlorides [7] or cyclization with amic acids.[8] On the other hand,
progresses on catalytic aminocarbonylation have been achieved
based on the use of different transition metals, such as Pd,[9]
Fe[5a,10], Co[11], Ru[12], Rh[11c,13], Sn[14] etc. Notably, the seminal
work of Beller showed the beneficial use of diamine type ligands
in iron carbonyl catalysis and the reactions were allowed to be
performed under relative mild conditions.[10c] However, in this
case, excess amounts of amine substrates (ten equivalents) were
necessary to achieve reasonable yields. Therefore, further
improvement for iron-carbonyl catalyzed aminocarbonylation is
still required. Hence, the discovery of novel catalysts or co-
esters[16b] and in nickel-catalyzed coupling reactions between β,β-
difluoro-styrenes and alkynes.[16e] In continuation of our interest in
carbonylation of olefins and alkynes,[1f,1g] we extended the work to
aminocarbonylation and anticipated that ZrF4 might be superior
compared to the promotion effect of phosphine or nitrogen ligands
in carbonylation reactions, considering
the possible
zirconium···iron and F···H-N affinity effect. Herein, we describe
the first example of the use of ZrF4 as co-catalyst for
carbonylations to produce α,β-unsaturated amides (Scheme 1).
catalysts for this iron catalyzed reaction is highly desirable.
Functional fluoride-based inorganic materials have found
widespread applications in many fields including catalysis,
adsorption, electronics, and environmental technology.[15] It is
noteworthy that zirconium fluoride have been used as catalysts or
co-catalysts to effect various transformations.[16]
Scheme 1. ZrF4 as co-catalyst promoted iron-catalyzed aminocarbonylation.
In our initial studies, we investigated the aminocarbonylation of
phenylacetylene (1a) and cyclohexylamine (2a, CyNH2) as the
model reaction to test the promotion effect of fluoride containing
inorganic salts (Table 1). Firstly, the aminocarbonylation of
phenylacetylene (1a, 0.5 mmol) with CyNH2 (2a, 2.5 mmol) was
studied using Fe3(CO)12 as catalyst in toluene. The reaction
afforded 3aa in 21% yields (Table 1, entry 1). Subsequently, we
screened various fluoride containing inorganic salts (fluoride
salts of Cs, Cu, Fe, K, NH4, Zr, Li, Zn, Mg) in the presence of
Fe3(CO)12 (Table 1, entry 2-8, Table S1, entries 1-5). To our
delight, the addition of ZrF4 led to the desired N-substituted
cinnamide 3aa in 89% yield (Table 1, entry 8). In addition,
carrying out the reaction without Fe3(CO)12 resulted in undetected
[a]
Z. Huang, Y. Dong, YD. Li, Dr. M. Makha and Prof. Dr. Y. Li
State Key Laboratory for Oxo Synthesis and Selective Oxidation,
Suzhou Research Institute of LICP, Lanzhou Institute of Chemical
Physics (LICP), Chinese Academy of Sciences, Lanzhou 730000, P.
R. China.
E-mail: yhli@licp.cas.cn.
[b]
Z. Huang, Y. Dong, YD. Li
University of Chinese Academy of Sciences, Beijing 100049, P. R.
China.
Supporting information for this article is given via a link at the end of
the document.
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product, while substitution of Fe3(CO)12 with iron chlorides (FeCl2,
FeCl3) was ineffective (Table 1, entries 10-12). The use of
Fe2(CO)9 instead of Fe3(CO)12 as catalyst afforded the desired
product in only 56% yield for 3aa (Table 1, entries 13). Other
metal carbonyls (Cr, Mn, Co, Mo, Ru-based) were also examined
and found to be ineffective (Table S1, entries 6-10). Further
investigation into solvent effect resulted in lower yields (Table S1,
entries 11-13) while the use of polar solvent THF provided the
desired 3aa in 84% yield (Table 1, entries 14).
as tetrahydropyrrol (2j), piperidine (2k) as substrates resulted in
corresponding N-substituted cinnamides in high yields, (3aj, 82%)
and (3ak, 84%) respectively (Table 2).
Table 2. Carbonylation of phenylacetylene with different amines.[a]
Table 1. Aminocarbonylation reaction optimization conditions.[a]
Entry
[Fe]/ mol%
Additive/ mol%
Yield [%][b]
1
2
Fe3(CO)12/ 5
Fe3(CO)12/ 5
Fe3(CO)12/ 5
Fe3(CO)12/ 5
Fe3(CO)12/ 5
Fe3(CO)12/ 5
Fe3(CO)12/ 5
Fe3(CO)12/ 5
FeCl2/
-
CsF/ 5
21
5
3
CuF2/ 5
13
29
17
58
61
89
-
4
FeF2/ 5
5
FeF3/ 5
6
K2[VOF4(H2O)/ 5
[(NH4)3VO3F4/ 5
ZrF4/ 5
7
8
10
11
12
13
14[c]
ZrF4/ 5
FeCl3/
ZrF4/ 5
-
-
ZrF4/ 5
-
Fe2(CO)9/
Fe3(CO)12/ 5
ZrF4/ 5
56
84
ZrF4/ 5
[a] Reaction conditions: phenylacetylene (0.5 mmol), (CyNH2) (2.5 mmol),
Fe3(CO)12 (Fe: 5 mol%), additive (5 mol%), toluene (2 mL), CO (10 bar), 120 oC,
15 h. [b] The yield was determined by GC using n-tetradecane as an internal
standard. [c] THF (2 mL).
[a] Reaction conditions: phenylacetylene (0.5 mmol), amine (2.5 mmol),
Fe3(CO)12 (Fe: 5 mol%), ZrF4 (5 mol%), toluene (2 mL), CO (10 bar), 120 oC, 15
h, isolated yield. [b] no ZrF4.
With the efficacy of ZrF4 established and the optimized reaction
conditions in hand, we continued testing the generality of this
method. Therefore, we proceeded by screening the
aminocarbonylation reaction of various primary and secondary
amines with phenylacetylene in the presence of Fe3(CO)12 and
ZrF4. Gratifyingly, all attempts resulted in the desired N-
substituted cinnamides in good to excellent yields. The reactions
of cyclopentylamine, iso-propylamine, and tert-butylamine
afforded 3ab, 3ac and 3ad in 81%, 85% and 76% yields,
respectively (Scheme 2). Moderate reactivities were observed for
the desired N-substituted cinnamides from iso-butylamine (3ae,
71%) and propylamine (3af, 79%), whereas desired products
were obtained in higher yields from butylamine (3ag, 81%) and
hexylamine (3ah, 93%). It is noteworthy to mention that the
aminocarbonylation of phenylacetylene with benzylamine
resulted in moderate yield (3ai, 73%), in contrast to lower yield in
absence of ZrF4 (3ai, 38%). The use of secondary amines, such
Furthermore, in order to ascertain that the combination of
Fe3(CO)12 and ZrF4 is generally applicable to a broad range of
alkynes, we evaluated the aminocarbonylation of various alkynes
with amines. Aminocarbonylation reaction of piperidine (2k) with
aromatic alkynes afforded high yields for desired N-substituted
cinnamides. meta- and para-Substituted aromatic alkynes
showed insignificant directing electronic effects giving
comparable yields, and surprisingly the sterically hindered 1-
ethynyl-2-methoxybenzene (1e) provided the desired N-
substituted cinnamides in (3ek, 78%). Moreover, aromatic
alkynes bearing electron-withdrawing substituents such as fluoro
group have less influence on the product yield (3dk, 75%).
Similarly, aromatic alkynes with alkyl substitution afforded N-
substituted cinnamides in good yields (3bh, 76%; 3bl, 72%). To
our delight, aliphatic alkynes were also aminocarbonylated in
moderate to good yields, e.g., 3hk and 3ik. Interestingly, the
employed method catalyzes the reaction of internal alkynes in
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high yield, e.g., 3jk, 3kk, and 3lk in good to excellent yields (Table
3).
due to F···H-N hydrogen bonding interactions (Figure 2).[17]
Subsequently, to confirm activation patterns of Fe3(CO)12 by ZrF4,
a solution of Fe3(CO)12 and ZrF4 in toluene-d8 was prepared in the
presence of 13CO, heated to 60 °C and examined by NMR
analysis (Figure 3). From 13C NMR spectrum of the mixture, a new
signal appeared at δ = 210.5 ppm (C2) indicating the formation of
mononuclear iron carbonyl Fe(CO)5 promoted by ZrF4 (Figure 3,
b and c).[18a] Noteworthy to mention that Fe3(CO)12 without ZrF4
was unaffected under same conditions (δ = 212.3 ppm; C1).[18b]
Table 3. Carbonylation of different alkyne with different amines.[a]
Figure 2. 1H NMR spectra of the CyNH2 (a), CyNH2 and ZrF4 (b) (In toluene-d8,
(a) and (b) were heated at 60 °C for 2 h, respectively).
Figure 3. 13C NMR spectra of the Fe3(CO)12 (a), Fe3(CO)12 and ZrF4 (b),
Fe3(CO)12 and ZrF4 (c) (In toluene-d8, a, b and c NMR runs were subjected to
heated up to 60 °C for 2h,1h and 2h; respectively).
[a] Reaction conditions: phenylacetylene (0.5 mmol), amine (2.5 mmol),
Fe3(CO)12 (Fe: 5 mol%), ZrF4 (5 mol%), toluene (2 mL), CO (10 bar), 120 oC, 15
h, isolated yield. [b] Z/E =1.2/1.
In order to understand the promotion effect of fluoride salts, NMR
studies were devised to gauge ZrF4 interactions with the amine
substrate and Fe3(CO)12 catalyst. Accordingly, in-situ NMR
experiments using 13C-labelled carbon monoxide in toluene-d8
were performed. Initially, NMR spectra were recorded
independently on binary mixtures: cyclohexylamine with ZrF4 and
Fe3(CO)12 with ZrF4. From the H NMR spectrum of CyNH2 with
ZrF4, we found that amine protons’ signal of CyNH2 ( 0.63 ppm)
are greatly affected by ZrF4 and shifted downfield ( 5.58 ppm)
Figure 4. 13C NMR spectra of the reactions using Fe3(CO)12 and ZrF4. 1 bar
13CO, room temperature to 60 oC in toluene-d8.
To gain further insights, we performed in-situ NMR experiments
in toluene-d8 for the reaction of phenylacetylene and CyNH2 using
13C-labelled CO (1 bar) in the presence of Fe3(CO)12 and ZrF4 at
1
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suspension was concentrated in vacuo and the residue was purified by
flash chromatography on silica gel to provide (cyclohexyl)cinnamamide,
3aa. Purified by flash chromatography on silica gel (PE: EtOAc = 3:1).
yield: 78%, white solid, m.p. 107-108 °C. 1H NMR (400 MHz, CDCl3) δ 7.65
(d, J = 15.6 Hz, 1H), 7.49-7.41 (m, 2H), 7.37-7.33 (m, 3H), 6.54 (d, J =
15.6 Hz, 1H), 6.33 (d, J = 7.5 Hz, 1H), 4.02-3.85 (m, 1H), 2.01-1.98 (m,
2H), 1.75-1.63 (m, 3H), 1.46-1.31 (m, 2H), 1.31-1.11 (m, 3H). 13C NMR
(100 MHz, CDCl3) δ 165.2, 140.5, 135.0, 129.5, 128.8, 127.7, 121.5, 48.5,
33.2, 25.6, 25.0.
different temperatures (Figure 4; full spectra and detailed reaction
conditions described in the SI). Initially, in-situ NMR experiments
showed no signal for 13C-labelled CO or Fe3(CO)12 while a new
signal appeared at δ = 210.5 ppm corresponding to the immediate
formation of 13C-labelled Fe(CO)5 even at 25 oC (Figure 4a). Upon
heating to 60 oC, a new signal appeared at δ = 217.2 ppm (Figure
4b,c), which might be ascribed to the iron carbonyl coordinated by
substrate molecules formed under heating conditions (Figure
4).[10b,18,19] On the basis of the above experimental results, and
literature reports on iron carbonyls catalyzed aminocarbonylation
17, 18,
reactions[10,
19], a possible reaction pathway could be
Acknowledgements
rationalized. Firstly, the active mononuclear iron carbonyl
Fe(CO)5 was produced in-situ upon interaction of ZF4 with
Fe3(CO)12, followed by the amine and Fe(CO)5 interaction to
generate iron carbonyls complex [R’’NH2Fe(CO)4]. The iron
carbonyl complex reacts with the alkyne to yield acylcarbonyl iron
species. Subsequent CO insertion and reaction of ZrF4 activated
amine affords the final carbonylation product (Figure S10, SI).
Here, ZrF4 and Iron carbonyls species presumably work in concert
for the hydride transfer and hydrides were not detected during
NMR studies. Experimental data clearly showed ZrF4 was crucial
in the catalytic cycle as it acts on both iron carbonyls and amine
substrates.
We are grateful for the financial supports from NSFC (91745104,
21101109, 21602228) and NSF of Jiangsu Province
(BK20160394).
Conflict of Interest
The authors declare no conflict of interest.
Keywords: aminocarbonylation • ZrF4 • alkynes • iron-catalyzed
• α,β-unsaturated amides
In conclusion, we have demonstrated the first example of ZrF4
promotion towards iron catalyzed aminocarbonylation reaction. In
the presence of cheap and readily prepared ZrF4, various
aromatic and aliphatic alkynes including internal alkynes were
transformed into the desired α,β-unsaturated amides in good to
excellent yields. Preliminary mechanistic studies reveal that the
ZrF4 role influences F···H-N hydrogen bond and activation of
Fe3(CO)12. Further efforts to widen the applicability of this strategy
in other reactions are underway.
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General procedure: A mixture of Alkyne (0.5 mmol), amine (2.5 mmol),
Fe3(CO)12 (Fe 5 mol%), ZrF4 (10 mg), toluene (2 mL), and a stirring bar
were added into a vial (5 mL) in glovebox. After sealed, the vial was
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placed in an alloyed plate, which was then transferred into an autoclave
(250 mL) under nitrogen flow. At room temperature, the autoclave was
flushed with CO gas for five times and pressurized with CO gas to 10 bar.
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carefully released. The resulting suspension was concentrated in vacuo
and the residue was purified by flash chromatography on silica gel to
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COMMUNICATION
COMMUNICATION
Zijun Huang, Yanan Dong, Yudong Li,
Mohamed Makha and Yuehui Li*
Page No. – PPage No. – Page No.
Enhancing Ligand-free Fe-Catalyzed
Aminocarbonylation of Alkynes by
ZrF4
We have demonstrated for the first time the exceptional promotion effect of ZrF4
towards iron catalyzed aminocarbonylation reaction. In the presence of cheap and
readily available ZrF4, various aromatic and aliphatic alkynes are transformed into
the desired α,β-unsaturated amides in good to excellent yields.
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