Palladium-catalyzed selective generation of CO from formic acid for carbonylation of alkenes

Article abstract of DOI:10.1021/jacs.8b01123

A general and selective palladium-catalyzed alkoxycarbonylation of all kinds of alkenes with formic acid (HCOOH, FA) is described. Terminal, di-, tri-, and tetra-substituted including functionalized olefins are converted into linear esters with high yields and regioselectivity. Key-to-success is the use of specific palladium catalysts containing ligands with built-in base, e.g., L5. Comparison experiments demonstrate that the active catalyst system not only facilitates isomerization and carbonylation of alkenes but also promotes the selective decomposition of HCOOH to CO under mild conditions.

Full text of DOI:10.1021/jacs.8b01123

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Palladium-catalyzed Selective Generation of CO
from Formic Acid for Carbonylation of Alkenes
Rui Sang, Peter Kucmierczyk, Kaiwu Dong, Robert Franke,
Helfried Neumann, Ralf Jackstell, and Matthias Beller
J. Am. Chem. Soc., Just Accepted Manuscript • DOI: 10.1021/jacs.8b01123 • Publication Date (Web): 12 Mar 2018
Downloaded from http://pubs.acs.org on March 12, 2018
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Journal of the American Chemical Society
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Palladium-catalyzed Selective Generation of CO from Formic
Acid for Carbonylation of Alkenes
Rui Sang,† Peter Kucmierczyk,†‡ Kaiwu Dong,† Robert Franke,‡§ Helfried Neumann,† Ralf Jackstell,†
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and Matthias Beller*,†
†Leibniz-Institut für Katalyse e.V. an der Universität Rostock, Albert-Einstein-Str. 29a, Rostock, 18059, Germany
‡
Lehrstuhl für Theoretische Chemie, Ruhr-Universität Bochum, 44780 Bochum, Germany
§Evonik Performance Materials GmbH, Paul-Baumann-Str. 1, 45772 Marl, Germany
KEYWORDS: formic acid • carbonylation • CO surrogate • esters • palladium.
ABSTRACT: A general and selective palladium-catalyzed alkoxycarbonylation of all kinds of alkenes with formic acid (HCOOH,
FA) is described. Terminal, di-, tri-and tetra-substituted including functionalized olefins are converted into linear esters with high
yields and regioselectivity. Key-to-success is the use of specific palladium catalysts containing ligands with built-in base, e.g. L5.
Comparison experiments demonstrate that the active catalyst system not only facilitates isomerization and carbonylation of alkenes,
but also promotes the selective decomposition of HCOOH to CO under mild conditions.
HCOOH by dehydration in the presence of strong mineral
acids (e.g. sulfuric acid; Morgan reaction), but these condi-
INTRODUCTION
[16]
tions are not compatible with most carbonylation reactions.
Carbonylation reactions constitute powerful tools to synthesize
carboxylic acids and their derivatives both in industry and
academic organic synthesis. In general, these processes make
To use HCOOH as an inexpensive and less toxic surrogate
for carbonylations, acetic anhydride has been added to gener-
ate the more reactive mixed anhydride in situ. Following this
strategy, Shi and co-workers demonstrated effective palladium-
[1]
use of toxic and flammable CO under (high) pressure, which
requires specific equipments and safety measures. To over-
come these problems, substantial attention has been paid to
the development of carbonylation reactions with so-called CO
[10]
[17]
catalyzed hydroformylation
and hydrocarboxylation
of
terminal alkenes. However, comparably high catalyst loadings
(3-5 mol%) have to be employed in this case. Notably, indus-
trially important internal alkenes did not work under these
conditions. Hence, to the best of our knowledge, the selective
alkoxycarbonylation of internal alkenes to give linear esters
using HCOOH has not been explored yet (Scheme 2).
[2]
surrogates. Representative examples include transition-metal
[3]
catalyzed olefin carbonylations with metal carbonyls, acyl
[4]
[5]
chlorides, formic acid (HCOOH) or its derivatives, para-
[6]
[7]
formaldehyde, and even CO2 . Among all of these CO
substitutes, formic acid is probably the most convenient C1
source, readily available from the fermentation of bio-waste
[8]
[9]
.
or via catalytic hydrogenation of CO2
Scheme 2. Catalytic alkoxycarbonylation of olefins.
Scheme 1. Formic acid decomposition pathways.
[10]
[11]
Thus, carbonylations of alkenes and alkynes as well as
aryl and alkenyl (pseudo) halides using HCOOH have been
investigated, albeit with moderate successes in the presence of
[12]
[13]
rhodium, iridium , and ruthenium complexes. A general
Obviously, to achieve such a transformation, the selective
decomposition of formic acid to CO has to be combined with
the efficient isomerization and alkoxycarbonylation of alkenes
in one process (Scheme 3). Herein, we present palladium-
based catalyst systems with special ligands, which for the first
time are able to catalyze all these steps efficiently. Optimal
problem for the effective use of HCOOH in these reactions is
its unspecific decomposition to give both CO and water or
hydrogen and CO2 (Scheme. 1)
geneous catalysts are known to catalyze the latter decomposi-
tion, the former transformation is difficult to achieve selec-
tively at low temperature. Clearly, CO can be released from
[9b, 14]
. While numerous homo-
[15]
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results for linear esters from sterically hindered alkenes and
formic acid are obtained in the presence of the new ligand L5.
the generation of the active palladium hydride complex, is
ascertained by the control experiment without PTSA (Table 1,
entry 12).
1
2
3
4
5
6
Scheme 3. Domino carbonylation catalysis: Hydroes-
terification of sterically hindered alkenes with
HCOOH.
Table 1. Alkoxycarbonylation of 2,3-dimethyl-2-
butene 1a with HCOOH: Effect of ligands, palladium
[a]
precursors and acids.
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RESULTS AND DISSCUSSION
Initially, the Pd-catalyzed methoxycarbonylation of tetra-
methylethylene 1a using HCOOH was investigated in the
presence of different ligands. Typically, reactions were carried
o
out with Pd/ligand/PTSA ratio of 0.25/1/4 mol% at 100 C
Entry
L
Pd source
Acid
2a/Yield%[b] 3a/Yield%[b]
for 13 h in a sealed tube. As depicted in Table 1, regular lig-
ands Xantphos L1 and DPEphos L2, which are known to
catalyze the hydrocarboxylation of olefins using HCOOH in
the presence of acetic anhydride, gave no desired ester 2a and
substantial amounts of byproducts 3a were formed in both
cases (Table 1, entries 1 and 2). Notably, 2-methoxy-2,3-
dimethylbutane results from the simple acid-catalyzed etherication
of the olefin, while 2,3-dimethylbutan-2-ol is a result of the subse-
1
L1
L2
L3
L4
L5
L6
L5
L5
L5
L5
L5
L5
L5
L5
L5
L5
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(acac)2
PdCl2
PTSA
PTSA
PTSA
PTSA
PTSA
PTSA
PTSA
PTSA
PTSA
PTSA
PTSA
0
0
30
34
22
13
13
27
13
29
27
24
10
1
2
0
3
32
62
67
10
65
0
4
t
5
quent hydrolysis. On the other hand, L3 (d bpx), which is cur-
rently used in industry for alkene alkoxycarbonylation,
[18]
6
afforded the desired product in moderate yield (32%; Table 1,
entry 3). Recently, we modified this type of ligand by introduc-
ing basic heterocycles on the P-atom (e.g. L4, L5 and L6),
7
[19]
8
which led to improved catalysts. Indeed, when the bench-
mark reaction was performed with L4, the linear ester was
obtained in 62% yield (Table 1, entry 4). Even better results
were observed using the new ligand L5 and 2a was obtained
in 67% yield (Table 1, entry 5). The low yield (10%) of 2a in
the presence of L6 revealed the importance of the backbone in
the ligand (Table, entry 6). Other well-known mono- and bi-
dentate phosphine ligands such as PPh3, dppf, Naphos, etc.
(L7-L14) were also explored, but in no case any product was
observed under identical reaction conditions (see Table S1 in
the supporting information).
9
Pd2(dba)3
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
7
10[c]
11[d]
12
13
14
15
16[e]
36
48
6
CF3SO3H
CH3SO3H
H2SO4
PTSA
PTSA
PTSA
60
65
59
81
93
97
13
12
14
9
Further investigations of the reaction conditions applying
the optimal ligand L5 revealed a substantial effect of the palla-
dium precursor, the ratio of MeOH/HCOOH, and the type
of acid co-catalyst. Specifically, a similar yield (65%) of 2a was
got by using Pd(acac)2 , other palladium salts including PdCl2,
Pd2(dba)3 did not catalyze this transformation efficiently and
less than 7% yield of 2a was detected (Table 1, entries 7-9).
Reducing the amount of HCOOH (MeOH/HCOOH,
1.8/0.2 mL), the yield of the desired product also decreased to
36% (Table 1, entry 10), which might be explained by the
slower generation of CO. On the other hand, carrying out the
benchmark reaction in MeOH/HCOOH (1.0/1.0 mL), the
yield of the desired ester dropped to 48% (Table 1, entry 11).
The necessity of the acid co-catalyst, which is responsible for
17[e, f] L5
1
18[e,
trace
L5
g]
[a] Reaction conditions: 1a (2.0 mmol), [Pd] (0.25 mol%), L
(1.0 mol%), acid co-catalyst (4.0 mol%), MeOH/HCOOH
(1.5/0.5 mL), 100 oC, 13h; by-products 3a is a mixture of 2-
methoxy-2,3-dimethylbutane and 2,3-dimethylbutan-2-ol.[b]
Determined by GC analysis using iso-octane as internal standard.
[c] MeOH/HCOOH (1.8/0.2mL). [d] MeOH/HCOOH
(1.0/1.0 mL). [e] 20 h [f] [Pd]/L/acid (0.5/2/8 mol%). [g]1a
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(1mmol), [Pd]/L/acid (1/4/16 mol%). PTSA: p-toluenesulfonic
1a was converted within 7 hours. After that time, the turnover
number for CO gas formation is TONco = 279 (see SI). In the
first 20 minutes, almost all the consumed 1a is transformed
into internal alkene 1ab and the corresponding ether or alco-
hol 3a and only traces of the desired product 2a are formed.
Performing the reaction for 20 minutes in a sealed glass tube
gas formation can be already observed (Figure 3). After that
time, gas formation in the autoclave increased in a linear
manner. In contrast, the yield of the internal alkene 1ab,
reached a maximum after 20 minutes (6%) and then is re-
duced due to the relatively faster methoxycarbonylation.
Hence, after 5 hours only traces of this intermediate are de-
tected. Similarly, the yield of 3a increased in the initial phase
of the reaction and after 90 minutes, started decreasing again
to the end. The yield of the desired product 2a constantly
increased after the initial first 20 minutes. Notably, comparing
concentrations of substrate 1a and the undesired by-product
3a, the later compound is always the less. Hence, we conclude
the isomerization of the notoriously unreactive internal olefin
1a to the more reactive terminal alkene 1ab is the slow (key)
step in this process.
acid (monohydrate).
1
2
3
4
5
6
7
8
Apart from PTSA, other types of strong acids are also suita-
ble (Table 1, entries 13-15). Finally, the yield of 2a could be
increased to 97% with PTSA by optimization of the catalyst,
substrate concentration and extension of the reaction time
(Table 1, entry 18).
To understand the significant difference in reactivity of our
special ligands (L4, L5) with “built-in base” compared to other
well-known phosphines, we performed control experiments for
the decomposition of HCOOH to CO in MeOH/HCOOH
(6.5/1.5 mL, 40 mmol FA) at 100 °C for 18 h. As shown in
Figure 1, no or very little conversion (less than 0.5 bar of pres-
sure generated) was observed using Pd(OAc)2, PTSA or a
mixture of these reagents. Surprisingly, in the presence of
Pd(OAc)2 and L3 strong gas formation occurred resulting in
8.6 bar pressure. However, gas chromatographic measure-
ments showed that similar amounts of carbon dioxide and
carbon monoxide (58:42) were formed. Notably, using ligand
L4 instead of L3, in which a tertiary butyl substituent on every
phosphorous atom is replaced by pyridine base, selective for-
mation of CO took place and 2.2 bar of pressure was generat-
ed (CO vs CO2 = 82:18). When Pd(OAc)2/L4 was applied
together with PTSA (0.05/0.2/1 mol%) both high activity and
selectivity was detected by GC analysis (5.5 bar, CO vs CO2 =
95:5). Apparently, the catalyst containing the built-in base
ligand allows for faster and more selective CO generation from
HCOOH. In agreement with this assumption, using a related
ligand L5 (Pd(OAc)2/L5/PTSA), 6.0 bar of gas with 92%
selectivity of CO (CO vs CO2) was produced in the autoclave.
To the best of our knowledge, [Pd]/L4/PTSA or
[Pd]/L5/PTSA constitute the first homogeneous metal cata-
lysts allowing such selective formation of CO directly from FA
under comparably mild conditions.
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Yield/%
100
pressure/ba
14
1a%
1ab% yield
2a% yield
3a% yield
pressure bar
90
80
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50
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10
0
12
10
8
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4
2
0
0
60
120
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480
Time/min
P/bar
CO2
H2
CO
6
5
4
Figure 2. Reaction pathways of the methoxycarbonylation of 1a
using formic acid as CO surrogate. Reaction conditions: 25 mL
autoclave, Pd(OAc)2 (0.7 mol%), L5 (2.8 mol%), PTSA (11.2
mol%), 1a (1.0 mL, 8.5 mmol), iso-octane (0.5 mL), HCOOH (3.0
mL), MeOH (9.0 mL), 100 oC.
3
2
1
0
Figure 1. Control experiments on the catalytic decomposition of
HCOOH to CO, H2, and CO2. Reaction conditions: 25 mL
autoclave, Pd(OAc)2 (0.02 mmol), L5 (0.08 mmol), PTSA (0.4
mmol), HCOOH (1.5 mL), MeOH (6.5 mL), 100 oC, 18 h.
20
20 h
To gain further mechanistic information on the rate of the
individual steps of this domino transformation, the methox-
ycarbonylation of 2,3-dimethyl-2-butene 1a using formic acid
was investigated in more detail. As shown in Figure 2, 92% of
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Figure 3. Methoxycarbonylation of 1a using formic acid in a
sealed glass tube. Reaction conditions: 35 mL glass tube,
Pd(OAc)2 (1.0 mol%), L5 (4.0 mol%), PTSA (16.0 mol%), 1a (1.0
mmol), iso-octane (0.1 mL), HCOOH (0.5 mL), MeOH (1.5 mL),
100 oC.
1
2
3
4
5
6
Scheme 5. Proposed mechanism.
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Under acidic contions formic acid and methanol easily form
methyl formate(MF), which might also act as CO-releasing
agent. To better understand the influence of MF in our reac-
tion, comparison experiments using MF and FA were investi-
gated (see SI, Scheme S1). In the presence of FA the desired
product 2a was obtained in 64% yield under standard condi-
tions, while using the same amount of MF only the unwanted
ether 3a was observed. Notably, adding MF and water, which
allows hydrolysis to FA, 2a was formed again. As shown in
Scheme 4, the reaction using MF as solvent without water
gave no desired product even after 20h, while in the presence
of only 0.2 mL water 2a is obtained in 97% yield (Scheme 4, a
and b). Interestingly, using FA and water without any metha-
nol present, hydroxycarbonylation occurred with similar effi-
ciency to give 4a in 92% yield (Scheme 4, c).
tion leads mainly to CO and H2O (Scheme 5, cyle A). As
shown in Figure 1 vide supra CO2 and H2 are formed to a
minor extent in the presence of [Pd]/L3/PTSA, or
[Pd]/L4 and [Pd]/L4/PTSA (Scheme 5, cyle B). Apparent-
ly, under acidic conditions the cationic [L2PdH] complex I
will more easily activate the C-H bond compared to the
+
Scheme 4. Comparison of Pd-catalyzed carbonylation
of 2,3-dimethylbutene with HCO2Me and FA.
On the basis of these studies and previous mechanistic inves-
[19(a), 20]
tigations
we propose the following mechanism (Scheme
+
5): Initially, formation of the cationic complex I [L2PdH]
takes place, which after formic acid coordination and activa-
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Entry
Alkene
Linear ester
Yield/% (n/iso)
1
2
3
[b]
[c]
1
95 (94/6)
4
5
6
7
8
[c]
2
3
95 (>99/1)
[c]
80 (75/25)
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[c]
4
5
6
7
93 (94/6)
Reaction condition: 35 mL glass tube, Pd(OAc)2 (1.0 mol%), L5
(4.0 mol%), PTSA (16.0 mol%), 1a (1.0 mmol), solvent, 100 C,
20h.
o
[c]
87 (92/8)
1g
more electropositive O-H bond in formic acid. After in situ
generation of CO and parallel isomerization of the internal
olefin 1a to the more reactive terminal alkene 1ab (Scheme 5,
cyle C), olefin coordination and insertion leads to the corre-
sponding alkyl complex IX. Subsequent CO insertion and
final necleophilic attack by methanol or water gives the prod-
uct and regenerates the active catalyst. It should be noted that
comparison experiments in Scheme 4 and Scheme S1 clearly
proof that the previously reported mechanism for Ru- and Pd-
catalyzed carbonylations of olefins using alkyl formates is not
[c]
91 (94/6)
(mixture of 1b, 1e, 1f)
90
93
94
96
94
(1/2 = 90/10)
8
[b]
88
(2/1= 87/13)
[5]
operating here (Scheme 5, cyle D) .
94 (>99/1)
96 (>99/1)
94 (>99/1)
96 (>99/1)
95 (>99/1)
94 (>99/1)
With optimized reaction conditions in hand, we investigated
the substrate scope for the Pd-catalyzed alkoxycarbonylation
reaction with formic acid and methanol (Table 2). Reactions of
terminal aliphatic alkenes such as 1-octene (1b), tert-butyl
ethylene (1c), and styrene (1d) proceeded efficiently with no
less than 80% yields and up to 99% linear selectivity (Table 2,
entries1-3). Internal alkenes as well as mixtures of internal and
terminal olefins are preferred for the industrial manufacture of
bulk chemicals due to their lower price. Therefore, olefin
isomerization followed by carbonylation is of significant inter-
est. Hence, we were pleased to see that this catalytic system is
able to convert aliphatic internal olefins, including 2-octene
(1e), 4-octene (1f) as well as the mixture of octenes (1g), into
the corresponding linear methyl nonanoate with high yields
and n-selectivity (Table 2, entries 4-6). Cyclic olefins such as
cyclopentene (1h), cyclohexene (1i), cycloheptene (1j), cy-
cloctene (1k) as well as indene (1l) and 1,2-
dihydronaphthalene (1m) were also transformed into the
desired esters in good yields and selectivities (Table 2, entries
7-8). The reactions of α-methylstyrene derivatives with various
substitutes on the phenyl ring (1n-1s) as well as α-
phenylstyrene (1t) and stilbene (1u) afforded a series of termi-
nal araliphatic esters in no less than 94% yields again with
excellent selectivities (Table 2, entries 9-11).
9
10
96 (>99/1)
[b]
[d]
11
97
[b]
12
95 (>99/1)
13
14
24 (>99/1)
90(>99/1)
15
16
32 (>99/1)
Table 2. Pd-catalyzed alkoxycarbonylation of alkenes
a
1a-1d’ with HCOOH.
[c]
90 (90/10)
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In summary, an operationally simple and general applicable
Page 6 of 8
1
2
3
4
5
6
7
8
protocol for the carbonylation of alkenes was developed. Ter-
minal, internal, tri- and even tetra-substituted as well as func-
tionalized olefins were converted efficiently into the desired
esters in high yields with good to excellent linear selectivity.
This advanced catalytic process relies: 1. on the selective cata-
lytic decomposition of HCOOH to CO and 2. the fast alkene
isomerization and regioseletive alkoxycarbonylation or hy-
droxycarbonylation in the presence of our palladium-
phosphine complexes with ligands L4 and L5. Considering the
readily availability of HCOOH, this powerful method pro-
vides an alternative for alkene carbonylation in both industry
and laboratory.
17
18
93 (>99/1)
47
[c]
19
20
90 (94/6)
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95 (>99/1)
ASSOCIATED CONTENT
Supporting Information
[b]
94 (>99/1)
[e]
21
[b]
87 (>99/1)
Additional experimental results and procedures and characteriza-
tion data. This material is available free of charge via the Internet
at http://pubs.acs.org.
[a] Reaction conditions: 1 (1.0 mmol), Pd(OAc)2 (1.0 mol%), L5
(4.0 mol%), PTSA(16.0 mol%),MeOH/HCOOH (1.5/0.5 mL),
100 oC, 20 h. GC yields using iso-octane as internal standard. [b]
isolated yields. [c] L3 instead of L5. [d] 40 h. [e] solvent: ROH
instead of MeOH, ROH/HCOOH (1.5/0.5 mL).
AUTHOR INFORMATION
Corresponding Author
* Matthias.Beller@catalysis.de
Furthermore, methoxycarbonylation of the industrial feed-
stock diisobutene (1v) proceeded via double-bond isomeri-
[21]
Notes
zation and consecutive carbonylation to produce selectively
the desired ester 2v in very good yield (Table 2, entries 12).
From a synthetic point of view it is important that various
functionalized olefins containing fluoride, silyl, imide, and
ester groups (1w-1a’) were tolerated. The desired esters were
achieved in up to 93% yields with high liear selectivities (Table
2, entries 13-17). Furthermore, methyl 2-acetamidoacrylate
(1b’) - an example of a notoriously unreactive push-pull olefin
- produced the corresponding amino acid derivative in 47%
yield (Table 2, entries 18).
The authors declare no competing financial interest.
ACKNOWLEDGEMENT
We thank for financial support from Evonik Performance
Materials GmbH and the State of Mecklenburg-Vorpommern.
The support of the analytical team of LIKAT is appreciated.
ABBREVIATIONS
FA, formic acid; MF methyl formate; Ad, adamantly; PTSA, p-
toluenesulfonic acid monohydrate; TON, turnover numbers.
The renewable internal ester 1c’ underwent the same isom-
erization/methoxycarbonylation transformation to provide the
diester in 90% yield and 94% n-selectivity (Table 2, entry 19).
Additionally, the dimethoxycarbonylated compound 2d’ was
obtained in 95% yield by carbonylation of 1d’ (Table 2, entry
20). Notably, carbonylation of 1a with EtOH or BuOH af-
forded the corresponding esters (2e’ and 2f’) in high yields
and selectivities (Table 2, entry 21). Finally, hydroxycarbonyla-
tion product 4a (Scheme 4) and 4b (Scheme 6) can be ob-
tained separately in 92% and 95% isolated yield. This process
demonstrates the possibility to obtain useful carboxylic acids in
a 100% atom-efficient way using formic acid!
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Palladium-catalyzed Selective Gener-
ation of CO from Formic Acid for
Carbonylation of Alkenes
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Let´s play domino. Palladium-catalyzed carbonylations of olefins with formic acid
proceeds in high yields and regioselectivities using phosphines with “built-in” base.
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