Revisiting the Palladium-Catalyzed Carbonylation of Allyl Alcohol: Mechanistic Insight and Improved Catalytic Efficiency

Article abstract of DOI:10.1021/acs.organomet.0c00117

Although crotonic acid (CA) is in high demand due to its use in various industrial applications, the preparation of CA currently requires a multi-step process from the petrochemical cracking of ethane with a very low overall yield and poor selectivity. An atom economical, one-step, carbonylation of readily accessible allyl alcohol to CA is one of the attractive approaches. In this study, the direct carbonylative transformation of allyl alcohol to CA was analyzed in detail to detect the reaction intermediates and propose a reaction mechanism. Following the reaction mechanism, the process was optimized to synthesize CA via the direct carbonylation of allyl alcohol with improved efficiency and productivity (TON = 420) under mild reaction conditions using Pd-based catalytic systems.

Full text of DOI:10.1021/acs.organomet.0c00117

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Revisiting the Palladium-Catalyzed Carbonylation of Allyl Alcohol:
Mechanistic Insight and Improved Catalytic Efficiency
Sudakar Padmanaban,‡ Jianwei Jiang,‡ and Sungho Yoon*
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ABSTRACT: Although crotonic acid (CA) is in high demand due to its use in various
industrial applications, the preparation of CA currently requires a multi-step process from
the petrochemical cracking of ethane with a very low overall yield and poor selectivity. An
atom economical, one-step, carbonylation of readily accessible allyl alcohol to CA is one of
the attractive approaches. In this study, the direct carbonylative transformation of allyl
alcohol to CA was analyzed in detail to detect the reaction intermediates and propose a
reaction mechanism. Following the reaction mechanism, the process was optimized to
synthesize CA via the direct carbonylation of allyl alcohol with improved efficiency and
productivity (TON = 420) under mild reaction conditions using Pd-based catalytic systems.
butane (dppb) as a catalytic system at 190 °C for 48 h
under 40 bar CO in dimethoxyethane (DME).17 Following
this, in-depth research and a comprehensive understanding of
the reaction mechanism are in demand to improve the
selectivity and productivity of CA synthesis. Additionally, a
detailed mechanistic study is crucial to develop additional
catalysts for this transformation.
INTRODUCTION
■
Crotonic acid (CA), an unsaturated carboxylic acid, is widely
used in the preparation of the active drug molecule,
Crotamiton, a scabicidal agent, as well as in the production
of cosmetics and hair styling products such as Cevian,
Mowilith, Gelva, and Vinac.1−5 In addition, CA derivatives
are used in the coating, plasticizer, adhesive, flocculant, and
agrochemical industries.1,4,6−8
The industrial synthesis of CA currently requires a multi-
step process with a very low overall yield (30%) that involves
the selective oxidation of crotonaldehyde, which is a byproduct
of the petrochemical cracking of ethane to ethylene.1,8,9 Given
the demand for CA, a facile and efficient method to produce
CA in high yields is desired. Various nonindustrial methods of
CA synthesis have been developed, including dehydration of 2-
hydroxybutyric acid, isomerization of 3-butenoic acid, oxy-
carbonylation of propene, bacterial fermentation, and pyrolysis
of poly(3-hydroxybutyrate).1,7,8 However, these procedures
often require harsh reaction conditions or result in poor
yields.7
From an industrial point of view, an atom economical, one-
step, carbonylative transformation of allyl alcohol to CA is an
attractive alternative to the above strategies because allyl
alcohol and carbon monoxide are readily accessible. However,
the poor leaving ability of the hydroxyl group and the H2O
byproduct causes poor selectivity,10 leading to the formation of
a mixture of products including unsaturated acids, butenoic
acid derivatives, cyclized lactones, and unsaturated esters
(Scheme S1).11−16 Thus, the carbonylation of allyl alcohol
derivatives, in general, suffers from obvious drawbacks, such as
high CO pressures, poor selectivity, or/and low yield.
Interestingly, Alper et al. reported the selective carbonylation
of allyl alcohol to CA in 93% yield with a turnover number
Therefore, in this study, to identify the reaction
intermediates, the carbonylation of allyl alcohol to CA was
1
monitored by H NMR spectroscopy under different time
intervals, and a mechanism for the reaction was proposed on
the basis of the intermediates observed during the process. In
addition, following the reaction mechanism, the reaction
conditions were optimized to produce CA with the highest
TON of 420 under low CO pressure (5 bar) at 110 °C in
benzene (Scheme 1).
Scheme 1. Pd-Catalyzed Carbonylation of Allyl Alcohol to
CA
Received: February 18, 2020
(TON) of 23.3 using Pd(dba)2 (dba
= bis-
(dibenzylideneacetone)) and 1,4-bis(diphenylphosphino)-
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a
Table 1. Pd(OAc)2-Catalyzed Carbonylative Transformation of Allyl Alcohol to CA in Different Solvents
selectivity (%)
b
entry
solvent
conversion (%)
γ-butyrolactone
allyl ester
3-butenoic acid
crotonic acid
TON for CA
1
2
3
4
5
benzene
dioxane
DME
THF
CH2Cl2
>99
>99
>99
>99
70
<1
ND
ND
2
ND
ND
<1
8
ND
ND
23
30
30
20
99
77
70
60
37
24
17
16
12
5
43
a
b
Reaction conditions: 0.1 M allyl alcohol (1 mmol, 10 mL of solvent), 4 mol % Pd(OAc)2, 4 mol % dppb, 50 bar CO, 110 °C, 18 h. Determined
1
using H NMR using mesitylene as an internal standard; TON for CA = mol of CA formed per mol of Pd.
RESULTS AND DISCUSSION
Table 2. Pd(OAc)2-Catalyzed Carbonylative
Transformation of Allyl Alcohol to CA
■
a
It has been reported that a catalytically active Pd0 complex can
be spontaneously formed from a PdII precursor in the presence
of phosphine ligands.18,19 Therefore, the allyl alcohol carbon-
ylation was initially performed with the readily available, air-
stable Pd(OAc)2 and dppb in different solvents under 50 bar
CO at 110 °C for 18 h in a 100 mL stainless steel tube reactor
(Table 1, entry 1−5). The crude carbonylation products from
b
c
entry CO (bar) T (°C) time (h) S/C CA yield (%)
TON
1
2
3
4
5
5
5
5
5
5
110
80
140
110
110
18
18
18
48
48
25
25
25
100
250
93
48
90
92
63
23.3
12.0
22.5
92.0
157.5
1
each reaction were analyzed by H NMR spectroscopy with
a
Reaction conditions: 1 mmol of allyl alcohol, 10 mL of benzene,
1
b
1
mesitylene as an internal standard. The H NMR spectral
ligand = dppb, Pd/dppb = 1:1. CA yield, calculated using H NMR
spectroscopy. TON = mol of CA formed per mol of Pd.
c
results showed that a mixture of products including CA, 3-
butenoic acid, allyl esters of CA and 3-butenoic acid, and γ-
butyrolactone (GBL) were formed in different ratios in
different solvents studied (Scheme S1). Interestingly, a 99%
conversion of allyl alcohol and 99% selectivity to CA was
observed upon using the nonpolar solvent benzene (Table 1,
entry 1). When ethereal solvents such as 1,4-dioxane,
dimethoxyethane (DME), and tetrahydrofuran (THF) were
used, the selectivity toward CA was decreased to 77, 70, and
60%, respectively (Table 1, entries 2−4). 3-Butenoic acid was
formed as the byproduct in both 1,4-dioxane and DME;
however, in the case of THF, along with 3-butenoic acid
(30%), the ally ester of CA (8%) and a negligible amount of
GBL (2%) were also formed. The use of CH2Cl2, a
noncoordinating polar solvent, resulted in a reduced
conversion (70%) and very low selectivity for CA (37%)
that was observed along with the formation of GBL (43%) and
3-butenoic acid (20%) (Table 1, entry 5). These byproducts
are believed to be the intermediates during the carbonylative
transformation of allyl alcohol to CA (vide infra). The large
excess of the ethereal solvents might interfere with the allyl
alcohol coordination to the Pd-site and might reduce the
reaction rate, resulting in the incomplete conversion of the
observed intermediates to CA. Whereas, the coordination of
allyl alcohol is expected to be facilitated in benzene and a
complete conversion of allyl alcohol to CA is observed.
However, the reason for the formation of GBL as a major
product in the CH2Cl2 solvent is currently not clear. Thus, for
the complete carbonylative transformation of allyl alcohol to
CA, benzene was used as the solvent in subsequent
experiments.
transformation of allyl alcohol to CA. At a slightly lower
temperature (80 °C), the yield of CA was reduced to 48% with
a TON of 12.0 (Table 2, entry 2). It is noticeable that
homogeneous Pd complexes tend to form Pd-black at elevated
temperatures. Similarly, the formation of Pd-black has been
observed frequently in Pd(OAc)2/dppb-catalyzed carbon-
ylation of allyl alcohol to CA (Figure S1).
In line with this, the TON for CA was reduced to 22.5 at a
higher temperature of 140 °C, due to undesired side reactions
and Pd-black formation (Table 2, entry 3). In this study, the
optimum reaction temperature was 110 °C.
To improve the productivity of the Pd(OAc)2/dppb
catalytic system, the substrate to catalyst (S/C) ratio was
increased from 25 to 100 and 250. Interestingly, a yield of 92%
CA with a TON of 92.0 was obtained with an S/C ratio of 100
in 48 h (Table 2, entry 4). Additionally, with an S/C ratio of
250, only a 63% yield of CA was obtained after 48 h, possibly
because of the gradual decomposition of active Pd-species into
Pd-black (Table 2, entry 5). Here, the use of heterogeneous
phosphine-based ligands as supports for the Pd precursors may
help to avoid both the aggregation of leached Pd metal and the
formation of Pd-black in the carbonylation reaction.
To further understand the mechanism of the conversion of
1
allyl alcohol to CA, detailed H NMR analysis of the reaction
mixture obtained at different time intervals was performed
using the Pd(OAc)2/dppb catalytic system at 5 bar CO in
benzene. Structures of the intermediates and product are
shown in Scheme 2, which were determined by comparing
their 1H NMR spectra to those of synthesized standard
samples or literature data. Peak assignments were made using
the structures shown in the inset of Figure 1 and in Figure S2.
Product amounts were estimated by integrating the area of the
peaks assigned to the corresponding products. In particular,
the content of allyl 3-butenoate, 3-butenoic acid, allyl
crotonate, CA, and allyl alcohol/ether were calculated
according to the integrated areas of peaks b, c, d, e, and a/f,
respectively (Figure 1 and Figure S2).
CA yield was unaffected by varying the CO pressure in the
range 5−50 bar; reactions at a low CO pressure (5 bar)
resulted in similar conversion rates (93% yield, TON = 23.3)
to those at a higher CO pressure (50 bar), under otherwise
identical reaction conditions (Table 2, entry 1). It may
originate from the fast CO insertion in this transformation, and
low CO pressure is enough to effectuate the transformation.
The reaction temperature significantly influenced the
reactivity and outcome of the Pd-catalyzed carbonylative
B
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Scheme 2. Structures of the Intermediates and Products Formed at Different Reaction Times during the Pd(OAc)2/dppb-
Catalyzed Carbonylative Transformation of Allyl Alcohol to CA
Figure 1. 1H NMR spectra of generated intermediates at different reaction times during the Pd(OAc)2/dppb-catalyzed carbonylative
transformation of allyl alcohol to CA.
After 1 h, the methene signal at 4.16 ppm (a) of allyl alcohol
disappeared, suggesting that almost all of the allyl alcohol was
consumed. Concurrently, new signals at 4.60 ppm (b), 4.63
ppm (d), and 3.05 ppm (c + c′) were detected, indicating the
formation of allyl 3-butenoate (52%), allyl crotonate (11%), 3-
butenoic acid (36%), respectively, as well as negligible CA
formation. As the reaction time extended to 3 h, the decreasing
relative intensity of the signal at 4.60 ppm suggested the
decomposition of allyl 3-butenoate. In addition, according to
signals at 3.05, 7.1, and 4.0 ppm, 3-butenoic acid (48%), CA
(27%), and allyl alcohol/ether (7%) were formed. As reaction
time increased further (>3 h), the ratio between the signals at
7.1 and 3.05 ppm gradually increased, indicating increasing CA
and decreasing 3-butenoic acid yields. The signal at 4.63 ppm,
attributable to allyl crotonate, remained at approximately 8%,
then started to decrease after 15 h. The complete conversion of
the intermediates into CA was observed after 18 h.
Figure 2. Product distribution for allyl alcohol carbonylation as a
function of reaction time.
Figure 2 shows the distribution of all possible products of
allyl alcohol carbonylation at different reaction times. Based on
these results and previous reports, a possible reaction
mechanism was proposed (Scheme 3). It is reported that
Pd0 species (1) is generated from the reduction of Pd(OAc)2
by phosphine ligand and CO at an elevated temperature.18−20
The oxidative addition of allyl alcohol to the Pd0 species 1
leads to the (π-allyl)palladium intermediate, 2, thus activating
the C−O bond in the allyl alcohol. The species 2 subsequently
rearranges to the alkyl-PdII intermediate 3.13 Then, the
coordination and insertion of CO with 3 lead to the formation
of the Pd-acyl intermediate 4. Reductive elimination of 4
affords 3-butenoic acid and regenerates the catalytically active
Pd0 species 1. The as-formed 3-butenoic acid undergoes
C
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Scheme 3. Proposed Reaction Pathway of Allyl Alcohol Carbonylation to CA
isomerization to drive the equilibrium toward the stable,
Table 3. Effect of Different Pd Sources on the Carbonylative
Transformation of Allyl Alcohol to CA
a
conjugated carboxylic acid CA via intermediate 6. The lower
21,22
bond dissociation energies (DH298
)
of C−O (∼80 kcal/
b
entry Pd precursor ligand S/C time (h) CA yield (%)
TON
mol) and C−H (∼90 kcal/mol) bonds in comparison with the
O−H bond of the allylic system (∼105 kcal/mol) and
carboxylic systems (∼112 kcal/mol) may facilitate the
activation of C−O and C−H bonds during the formation of
the species 1 and 5, respectively. The intermediates 3 and 4 are
in equilibrium with allyl ether and allyl-3-butenoate,
respectively, in the presence of allyl alcohol.
1
2
3
4
5
6
7
8
9
Pd/C
dppb
−
25
25
25
25
25
25
25
100
500
18
18
18
18
18
18
18
48
48
20
0
5.0
0
23.5
23.3
23.5
20
22.3
96.0
420.0
c
Pd(PPh3)4
Pd(PPh3)4
Pd2(dba)3
Pd(dba)2
Pd(PPh3)4
Pd(PPh3)4
Pd(PPh3)4
Pd(PPh3)4
dppb
dppb
dppb
dppe
PPh3
dppb
dppb
94
93
94
80
89
96
84
d
e
1
Based on the H NMR analysis results at different time
intervals and the proposed mechanism, the final step of the Pd-
catalyzed carbonylation of allyl alcohol to CA involves the
isomerization of 3-butenoic acid to CA. Therefore, the
isomerization of 3-butenoic acid to CA was then studied
using Pd(OAc)2/dppb as the catalyst. Interestingly, the 3-
butenoic acid was completely converted to CA within 2 h in
the absence of CO (Scheme S2). However, when 3-butenoic
acid was treated with dppb in the absence of a Pd species, no
isomerization was observed, indicating the importance of the
Pd species for the isomerization step.
From the above mechanism, the carbonylative trans-
formation of allyl alcohol to CA should also be catalyzed by
Pd0 precursors. Hence, to further confirm the reactivity of Pd0
as a catalytic species in the conversion of allyl alcohol to CA, a
series of Pd0 sources were investigated as catalysts (Table 3
and Figure S3).
Commercially available Pd/C was initially tested with allyl
alcohol and CO (5 bar) in the presence of dppb. The Pd/C-
dppb system produced only a 20% yield of CA, likely due to
the heterogeneous nature of the catalyst. Therefore, soluble
homogeneous Pd0 sources such as Pd(PPh3)4, Pd2(dba)3, and
Pd(dba)2 were investigated. However, in an initial trial with
Pd(PPh3)4 without the dppb ligand, no product was detected
(Table 3, entry 2). On the contrary, 94% CA formation was
observed during the carbonylation of allyl alcohol upon using
Pd(PPh3)4 along with dppb as a catalytic system (Table 3,
entry 3). Moreover, the other Pd0 precursors, such as
Pd2(dba)3 and Pd(dba)2, were also catalyzed the carbonylation
of allyl alcohol to CA upon being used in combination with
dppb with the formation of 90 and 93% of CA, respectively
(Table 3, entries 4 and 5). It has been reported that the
addition of the phosphine ligand assisted the heterolytic
cleavage of allyl alcohol into a cationic Pd-allyl intermediate
a
Reaction conditions: 1 mmol of allyl alcohol, 10 mL of benzene, 110
b
1
°C, 0.5 MPa CO, Pd/dppb = 1:1. CA yield, calculated using H
NMR spectroscopy. Reaction was performed without dppb. dppe =
bis(diphenylphosphino)ethane; Pd/dppe = 1:1. Pd/PPh3 = 1:2
c
d
e
and hydroxide anion in aqueous medium.23,24 In accordance
with the previous studies, these results suggest that the
addition of dppb may facilitate the formation and stabilization
of the corresponding (π-allyl)palladium intermediate 2 from
allyl alcohol in nonaqueous medium in the initial step. To
further confirm the effect of phosphine ligand, other
phosphine-based ligands such as bis(diphenylphosphino)-
ethane (dppe) and the monodentate ligand PPh3 were used
along with Pd(PPh3)4 in the carbonylation of allyl alcohol
(Table 3, entry 6 and 7). Interestingly, both the dppe and PPh3
were found to be comparatively active for the transformation
of allyl alcohol to CA with a conversion efficiency of 80 and
89%, respectively, which suggests that the addition of
phosphine ligands is needed for the initial allyl alcohol
activation. The higher catalytic activity found for the
Pd(PPh3)4/dppb system might originate from the effective
stabilization of the Pd-catalytic center by dppb ligand than the
other labile ligands such as dba or PPh3.
Thus, the Pd(PPh3)4/dppb catalytic system is highly
efficient for this transformation. Increasing the S/C ratio to
100 resulted in a 96% CA yield (Table 3, entry 8).
Additionally, a further increment in the S/C to 500 resulted
in a record high TON of 420.0 for the conversion of allyl
alcohol to CA in 48 h (Table 3, entry 9).
D
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Foundation of Korea (NRF) funded by the Ministry of
Science, ICT, and Future Planning, Republic of Korea.
CONCLUSIONS
■
In this paper, we have proposed simple and efficient catalytic
systems for preparing CA. The Pd0-dppb catalytic systems are
highly effective for the carbonylation of allyl alcohol to CA
under very low CO pressures. The system presented herein
affords excellent selectivity as well as desirable CA yields.
Detailed 1H NMR analysis of the reaction process reveals that
allyl alcohol is consumed rapidly and that the isomerization of
3-butenoic acid to CA plays a key role in driving the
equilibrium toward the target product. However, the formation
of Pd-black must be avoided to improve productivity in this
transformation. We propose that Pd-based catalysts show
promise for application in the industrial synthesis of CA
REFERENCES
■
(1) Blumenstein, J.; Albert, J.; Schulz, R. P.; Kohlpaintner, C.
Crotonaldehyde and Crotonic Acid. Ullmann’s Encyclopedia of
Industrial Chemistry; Wiley-VCH Verlag GmbH & Co. KGaA, 2005.
(2) Campain, C. Semipermanent hair shaping method. U.S. Patent
7,744,859B2, 2010.
̆
(3) Pulat, M.; Babayigit, D. Graft copolymerization of PU
membranes with acrylic acid and crotonic acid using benzoyl peroxide
initiator. J. Appl. Polym. Sci. 2001, 80, 2690−2695.
(4) Jasicka-Misiak, I.; Wieczorek, P. P.; Kafarski, P. Crotonic acid as
a bioactive factor in carrot seeds (Daucus carota L.). Phytochemistry
2005, 66, 1485−1491.
(5) Ute, K.; Asada, T.; Hatada, K. Highly “Diheterotactic”
Polymerization of tert-Butyl Crotonate. Macromolecules 1996, 29,
1904−1909.
EXPERIMENTAL SECTION
■
General Considerations. All reagents and materials used in this
study were obtained from commercial sources and were used as
received unless mentioned otherwise. The solvents used in this study
were dried using traditional methods. Conversions of allyl alcohol to
crotonic acid (CA) were determined by 1H NMR spectroscopy using
an Ascend 400 MHz instrument (Bruker).
General Procedure for Carbonylation of Allyl Alcohol. In a
glovebox, a solution of Pd(OAc)2 (9 mg, 0.04 mmol) and dppb (17
mg, 0.04 mmol) in 5 mL of benzene was charged to a homemade 100
mL stainless steel tube reactor and stirred at 20 °C for 20 min. Allyl
alcohol (58 mg, 1.0 mmol) dissolved in 5 mL of benzene was added,
then the reactor was flushed three times with CO and pressurized to 5
bar with CO. The autoclave was immersed in a preheated oil bath,
and the reaction mixture was stirred for 18 h at 110 °C. The pressure
was released after the reactor was cooled to room temperature and the
(6) Bassaid, S.; Chaib, M.; Bouguelia, A.; Trari, M. Elaboration and
characterization of poly (acrylic acid-co-crotonic acid) copolymers:
Application to extraction of metal cations Pb(II), Cd(II) and Hg(II)
by complexation in aqueous media. React. Funct. Polym. 2008, 68,
483−491.
(7) Farid, N. F. S. M.; Ariffin, H.; Mamat, M. R. Z.; Mohd Zahari, M.
A. K.; Hassan, M. A. Non-solvent-based pretreatment of poly(3-
hydroxybutyrate) for improved bio-based crotonic acid production.
RSC Adv. 2015, 5, 33546−33553.
(8) Mamat, M. R. Z.; Ariffin, H.; Hassan, M. A.; Mohd Zahari, M. A.
K. Bio-based production of crotonic acid by pyrolysis of poly(3-
hydroxybutyrate) inclusions. J. Cleaner Prod. 2014, 83, 463−472.
(9) Weissermel, K.; Arpe, H.-J. Oxidation Products of Ethylene.
Industrial Organic Chemistry; VCH Verlagsgesellschaft mbH, 1997; pp
143−190.
(10) Muzart, J. Palladium-catalysed reactions of alcohols. Part B:
Formation of C−C and C−N bonds from unsaturated alcohols.
Tetrahedron 2005, 61, 4179−4212.
(11) Alper, H.; Amer, I. A Simple and Mild Method for the Direct
Metal-Catalyzed Carbonylation of Allyl Alcohols to Acids. J. Mol.
Catal. 1989, 54, L33−L36.
(12) Naigre, R.; Alper, H. Palladium clay catalyzed regio- and
stereospecific synthesis of beta,gamma-unsaturated acids by the
carbonylation of allylic alcohols. J. Mol. Catal. A: Chem. 1996, 111,
11−15.
(13) Wu, F. P.; Peng, J. B.; Fu, L. Y.; Qi, X. X.; Wu, X. F. Direct
Palladium-Catalyzed Carbonylative Transformation of Allylic Alco-
hols and Related Derivatives. Org. Lett. 2017, 19, 5474−5477.
(14) Satoh, T.; Ikeda, M.; Kushino, Y.; Miura, M.; Nomura, M.
Palladium-Catalyzed Carbonylation of Allyl Alcohols in the Presence
of Phenols. J. Org. Chem. 1997, 62, 2662−2664.
1
crude reaction mixture was analyzed by H NMR spectroscopy.
ASSOCIATED CONTENT
* Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acs.organomet.0c00117.
■
sı
Schemes of possible products and isomerization path-
ways and figures of images of formations, H NMR
spectra, and effects of transformation (PDF)
1
AUTHOR INFORMATION
Corresponding Author
Sungho Yoon − Department of Chemistry, Chung-Ang
University, Dongjak-Gu, Seoul 06974, Republic of Korea;
orcid.org/0000-0003-4521-2958; Email: sunghoyoon@
cau.ac.kr
■
(15) Xiao, W. J.; Alper, H. Highly regioselective thiocarbonylation of
allylic alcohols with thiols and carbon monoxide catalyzed by
palladium complexes: A new and efficient route to beta,gamma-
unsaturated thioesters. J. Org. Chem. 1998, 63, 7939−7944.
(16) Liu, Q.; Wu, L.; Jiao, H.; Fang, X.; Jackstell, R.; Beller, M.
Domino Catalysis: Palladium-Catalyzed Carbonylation of Allylic
Alcohols to β,γ-Unsaturated Esters. Angew. Chem., Int. Ed. 2013, 52,
8064−8068.
Authors
Sudakar Padmanaban − Department of Chemistry, Chung-Ang
University, Dongjak-Gu, Seoul 06974, Republic of Korea
Jianwei Jiang − Department of Chemistry, Chung-Ang
University, Dongjak-Gu, Seoul 06974, Republic of Korea
Complete contact information is available at:
https://pubs.acs.org/10.1021/acs.organomet.0c00117
(17) Ali, B. E.; Alper, H. Lactonization of Unsaturated Alcohols
Catalyzed by Palladium Complexes under Neutral Conditions. J. Org.
Chem. 1991, 56, 5357−5360.
Author Contributions
(18) Amatore, C.; Blart, E.; Genet, J. P.; Jutand, A.; Lemaireaudoire,
S.; Savignac, M. New Synthetic Applications of Water-Soluble Acetate
Pd/Tppts Catalyst Generated in-Situ - Evidence for a True Pd(0)
Species Intermediate. J. Org. Chem. 1995, 60, 6829−6839.
(19) Amatore, C.; Carre, E.; Jutand, A.; M'barki, M. A. Rates and
Mechanism of the Formation of Zerovalent Palladium Complexes
from Mixtures of Pd(OAc)2 and Tertiary Phosphines and Their
Reactivity in Oxidative Additions. Organometallics 1995, 14, 1818−
1826.
‡S.P. and J.J. contributed equally to this work.
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
This work was supported by the C1 Gas Refinery Program
(2018M3D3A1A01018006) through the National Research
■
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(20) Amatore, C.; Jutand, A.; M'barki, M. A. Evidence of the
Formation of Zerovalent Palladium from Pd(OAc)2 and Triphenyl-
phosphine. Organometallics 1992, 11, 3009−3013.
(21) Blanksby, S. J.; Ellison, G. B. Bond Dissociation Energies of
Organic Molecules. Acc. Chem. Res. 2003, 36, 255−263.
(22) Kaur, R.; Hudson, B. M.; Draper, J.; Tantillo, D. J.; Anastasio,
C. Aqueous Reactions of Organic Triplet Excited States with
Atmospheric Alkenes. Atmos. Chem. Phys. 2019, 19, 5021−5032.
́
(23) Basset, J.-M.; Bouchu, D.; Godard, G.; Karame, I.; Kuntz, E.;
Lefebvre, F.; Legagneux, N.; Lucas, C.; Michelet, D.; Tommasino, J.
B. Heterolytic Splitting of Allylic Alcohols with Palladium(0)−TPPTS
in Water. Stabilities of the Allylphosphonium Salt of TPPTS and of
the Ionic Complex [Pd(η3-allyl)(TPPTS)2]+. Organometallics 2008,
27, 4300−4309.
(24) Kuntz, E.; Amgoune, A.; Lucas, C.; Godard, G. Palladium
TPPTS catalyst in water: C-allylation of phenol and guaiacol with allyl
alcohol and novel isomerisation of allyl ethers of phenol and guaiacol.
J. Mol. Catal. A: Chem. 2006, 244, 124−138.
F
https://dx.doi.org/10.1021/acs.organomet.0c00117
Organometallics XXXX, XXX, XXX−XXX