A robust multifunctional ligand-controlled palladium-catalyzed carbonylation reaction in water

Article abstract of DOI:10.1039/c8cc00324f

A novel, hydrophilic and recyclable methoxypolyethylene glycol (PEG)-modulated s-triazine-based multifunctional Schiff base/N,P-ligand L9 was prepared and used in Pd-catalyzed Heck-type carbonylative coupling reactions, affording diverse chalcone derivatives and 1,4-dicarbonyl esters in good yields.

Full text of DOI:10.1039/c8cc00324f

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Marilyn M. Olmstead, Alan L. Balch, Josep M. Poblet, Luis Echegoyenet al.
Reactivity differences of Sc3N@C2n (2n 68 and 80). Synthesis of the
first methanofullerene derivatives of Sc N@D5h-C80
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A Robust Multifunctional Ligand-controlled Palladium-Catalyzed
Carbonylation Reactions in Water
Received 00th January 20xx,
Accepted 00th January 20xx
Pei-Sen Gaoa,b, Kan Zhanga, Ming-Ming Yanga, Shan Xua, Hua-Ming Suna, Jin-Lei Zhanga, Zi-Wei
Gaoa*, Wei-Qiang Zhang a*, Li-Wen Xua,b
*
DOI: 10.1039/x0xx00000x
www.rsc.org/
Abstract
reaction suffers from unsatisfactory yields of chalcone
A novel, hydrophilic and recyclable methoxypolyethylene derivatives.1f Considering the general catalytic mechanism for
glycol (PEG)-modulated s-triazine-based multifunctional Pd-catalyzed carbonylative Heck reaction1i, it is not an easy
Schiff base/N,P-ligand L9 was prepared and used in Pd- task to achieve the transformation efficiently due to the
catalyzed Heck-type carbonylative coupling reactions, occurrence of several competing reactions, such as Heck
affording diverse chalcone derivatives and 1,4-dicarbonyl reaction and the formation of N,N’-diethylbenzamide via the
esters in good yields.
nucleophilic substitution of acyl-Pd intermediate with NEt3.
Therefore, it is essential to develop an efficient synthetic
α,β-Unsaturated ketones are key intermediates in the approach for this type of carbonylative Heck coupling reaction.
preparation of novel bioactive compounds. Particularly, From the standpoint of green chemistry, there is still room for
chalcone derivatives are an important class of flavonoids. They the development of a more environmentally benign catalytic
are traditionally prepared from simple aldehydes and ketones system for Heck-type carbonylative coupling reaction in water
via Claisen–Schmidt condensation under strong basic under a relatively low CO pressure. In other words, the
conditions. Undoubtfully, this is a robust method for the development of novel, recyclable, water-soluble and efficient
preparation of 1,3-diarylpropen-1-ones with a broad substrate catalytic system for carbonylative Heck reaction in aqueous
scope. However, it is still essential to develop general and phase is of significant interest. It is known that phosphine
efficient synthetic methods for α,β-unsaturated ketones, ligands often play a crucial role in Pd-catalyzed cross-coupling
especially unsaturated 1,4-dicarbonyl esters that have been reactions. Since Casalnuovo's pioneering report on the use of
rarely studied. Since the pioneering work of Heck and co- Pd(TPPMS)3 (TPPMS
¼
sodium diphenyl (3-sulfonato)
workers, Pd-catalyzed carbonylative Heck reaction has become phenylphosphine) for Suzuki, Heck, and Sonogashira couplings
one of the powerful methods for the preparation of complex of aryl halides in water/organic solvent mixtures, numerous
carbonyl compounds in the past few decades.1 Notably, most examples of hydrophilic phosphine ligands have been reported
carbonylative Heck reactions were achieved for intramolecular as effective cross-coupling catalysts. 3 These phosphine ligands
versions2 till 2010. Beller’s group in 2010 achieved
a
generally include: a) phosphines with anionic substituents,4 b)
5
challenging intermolecular Heck-type carbonylative coupling phosphines with cationic substituents, c) phosphines with
between aryl triflates and diverse vinyl-group containing neutral hydrophilic substituents, 6 d) phosphines supported on
compounds, producing an array of chalcone derivatives via water-soluble polymers.7
Pd/Dppp catalytic system for the first time.1g Next, Beller’s In recent years, we have reported several useful methods for
group developed a general method to access the similar the construction of s-triazine-derived donor-acceptor/donor-π-
compounds using a novel [(cinnamyl)PdCl]2 /bulky imidazolyl acceptor molecules starting from commercially available 1,3,5-
phosphine ligand catalytic system starting from commercially triazine chloride to develop a recyclable s-triazine-modified
available aromatic halides. However, this intermolecular N,P-ligands/Pd catalytic system for controllable allylation in
PEG-400.8 We believed that the exploration of novel water-
soluble and efficient ligands based on s-triazine could solve the
a.Key Laboratory of Applied Surface and Colloid Chemistry, Ministry of Education
(MOE) and School of Chemistry and Chemical Engineering, Shaanxi Normal
following problems: inefficiency of catalyst towards
carbonylative Heck reaction in aqueous media, non-
University, Xi’an 710062, P. R. China
Key Laboratory of Organosilicon Chemistry and Material Technology of Ministry
b.
recyclability of catalytic system, difficulty of separating
of Education, Hangzhou Normal University, P. R. China
Electronic Supplementary Information (ESI) available: [details of any
products from reaction mixtures. Herein, we report our recent
findings on the design and synthesis of a novel, hydrophilic and
supplementary information available should be included here]. See
DOI: 10.1039/x0xx00000x
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efficient methoxypolyethylene glycol modified s-triazine-based
multifunctional N,P-ligand for Pd-catalyzed carbonylative Heck
coupling reaction in water to afford novel α,β-unsaturated 1,4-
dicarbonyl esters.
Table 1. Discovery of a Pd-catalyzed ligand-controlled Heck carbonylation reaction in
watera
Entry
Derivation from standard conditions
none
Yield of 3a (%)
1
2
3
4
5
6
44
0
without Pd(OAc)2 or L1
when –OTf was replaced with –Cl, -Br or -I
NEt3 instead of Cs2CO3
0
11
90
7
1,4-dioxane instead of water
Dppp instead of L1
aConditions : 1a (0.2 mmol), 2a (0.6 mmol) and CO (5 bar) as substrates,
Pd(OAc)2 (2 mol%) and L1 (10 mol%) as catalyst, Cs2CO3 (0.6 mmol) as base
and water (0.5 mL) as solvent. The reaction was performed at 95°C.
Initially, we evaluated a model reaction of phenyl triflate 1a
,
with styrene 2a (3 equiv) in the presence of CO using different
Pd(OAc)2/ligand catalytic systems. Under the standard
conditions, the desired product 1,3-di-phenylpropen-1-one
was obtained in 44% yield (Table 1, Entry 1). However, N,N’-
dimethylbenzamide (25% yield) and Heck coupling products
(trace amounts) were detected. When ligand L1 or Pd catalyst
was not used, no carbonylative product was obtained (Table 1,
Entry 2). Because N,N’-dimethylbenzamide was formed due to
the decomposition of NEt3 (Table 1, Entry 4), other bases were
used in place of NEt3 (Table S1). To our delight, Cs2CO3 was
superior to other bases, affording 1,3-diphenylpropen-1-one in
90% yield. When phenyl halides (-Cl, -Br, -I) were used as
substrates, no desired product was obtained (Table 1, Entry 3).
Interestingly, when 1,4-dioxane was used as the solvent
instead of water, the yield of desired 1,3-diphenylpropen-1-
one dramatically increased to 90% probably because of the
stability of Pd/L1 catalyst in organic solvents. Other ligands
were also screened in the titled reaction (Table S4). Notably,
When Dppp was used as a ligand in this reaction, the product
was obtained in only 7% yield (Table 1, Entry 6).
Scheme 1. Relationship between the catalytic performance and ligand structure under
general conditions (Table 1, entry 5).
Based on the investigation of the relationship between the
catalytic performance and structure of imine-phosphine
ligands, we hypothesized that the yield of carbonylative Heck
coupling reaction in water would be improved by introducing
hydrophilic groups into the s-triazine core. One simple strategy
is the replacement of –Cl group in L2 by a water-soluble
methoxypolyethylene glycol unit. Therefore, the nucleophilic
substitution of L2 with ethylene glycol was performed under
strong basic conditions. The desired product L9
(methoxypolyethylene glycol 2000 grafted s-triazinal N,P-
ligand) was obtained in 77% yield . The procedure for the
preparation of L9 is shown in scheme 2. In the first step, 1,3,5-
triazine chloride reacted with MeOH, furnishing S2 in 80% yield.
Then, the second Cl atom was substituted with o-
phenylenediamine via Pd-catalyzed Buchwald–Hartwig
reaction, affording S3 in 55% yield. L2 was obtained via
To better understand the relationship between catalytic
performance and ligand structure, we modified the
substitution pattern of s-triazine and evaluated the catalytic
performance of the titled reaction in 1,4-dioxane (Scheme 1).
Both L1 and L4 afforded the desired product in good yields,
90% and 88% respectively. However, L2 bearing a –Cl group
could not afford the desired product. When L5 was used in the
reaction, the targeted product was obtained in only 33% yield.
Without a phosphine unit in the ligand, for example L7, no
desired product was obtained. Biphosphine ligand L5 could
afforded 3a in 81% yield. Without the help of the s-triazine
core, for example, L6, a slight amount of 3a was obtained.
condensation
of
S3
and
DPPBde
Finally,
(2-(diphenyl-
water-soluble
phosphino)benzaldehyde).
methoxypolyethylene was attached to L2 via nucleophilic
substitution under strong basic conditions, producing L9 in a
moderate yield. FT-IR, 31P-NMR, and elemental analyses clearly
showed that L2 unit was successfully grafted with
methoxypolyethylene glycol 2000 (Figs. S2 and S3).
2 | J. Name., 2012, 00, 1-3
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3g, and 3o in poor yields, 44 %, 35 % and 38%, respectively.
Using the catalyst Pd(OAc)2/L9, chalcones bearing thiophenyl
groups, such as 3k and 3m, were obtained in 85% and 81%
yields, respectively.
To check the recyclability of catalyst Pd(OAc)2/L9 in water, the
carbonylative Heck coupling of phenyl triflate 1a, CO and
styrene was examined in the presence of 2 mol% Pd(OAc)2 and
10 mol% of L9. The catalytic system could be reused for five
times and the yields of 3a in each run were 90%, 82%, 82%,
75% and 63%. Because of the loss of activated Pd species, the
yield of 3a obviously decreased to 63% after five runs.
Nevertheless, we believe that it is the first example of a
recyclable Pd catalyst for carbonylative Heck reaction in water.
Next, we evaluated the reaction performance of phenyl
triflates and methyl acrylate using Pd(OAc)2/L9 catalyst system
under 5 atm of CO. Product 5a was obtained in 90% yield and a
1
slight amount of benzoic anhydride was monitored by H-NMR
analysis. Then the substrate scope of this reaction was
evaluated using various acrylates and substituted phenyl
triflates (Table 2). Phenyl triflates with –pCl (1i), –pMe (1h and
1j), –pCF3 (1l), –pOMe (1f and 1g) groups afforded the desired
products in good yields. Acrylate bearing -Me (5a), -Et (5b, 5i,
Scheme 2. Synthetic routes of L9 starting from 1,3,5-triazine chloride.
5j), -nBu (5c), -iBu (5d), -Ph (5f
, 5h) and -Bn (5e, 5g) are well
tolerated in the reaction. Furthermore, Pd(OAc)2/L9 catalytic
system could also be applied in the carbonylative Heck
coupling with α-methyl substituted acrylates. Under the
optimized conditions, 5m and 5n could be obtained in
moderate yields, 71% and 70%, respectively.
Table 2. Substrate scope of Pd-catalyzed carbonylative Heck reaction with styrenes.
Table 3. Substrate Scope of Pd-catalyzed carbonylative-Heck reaction with acrylates
Entry
Ar1
Ar2
Product
Yield of 3 (%)
1
2
Ph
(p-OMe)Ph
(o-OMe)Ph
(p-Br)Ph
Ph
3a
3b
3c
3d
3e
3f
85
82
81
88
86
44
35
77
80
82
85
86
81
77
38
78
73
75
Ph
Ph
3
4
Ph
5
(p-Br)Ph
(p-OMe)Ph
Ph
6
(p-NO2)Ph
(p-F)Ph
7
Ph
3g
3h
3i
8
Ph
(p-Ph)1,3-dienyl
Ph
Entry
1
R1
H
R2
Me
Et
nBu
iBu
Bn
R3
H
Product
5a
Yield of 5 (%)
9
2-naphthol
(p-OMe)Ph
m-thiophenyl
(p-OMe)Ph
m-thiophenyl
(m-Cl)Ph
90
88
85
88
82
80
80
88
90
91
88
91
71
70
10
11
12
13
14
15
16
17
18
(p-OMe)Ph
Ph
3j
2
H
H
5b
5c
3k
3l
3
H
H
(m-NO2)Ph
(p-Me)Ph
(p-F)Ph
(m-NO2)Ph
Ph
4
H
H
5d
5e
3m
3n
3o
3p
3q
3r
5
H
H
6
p-OMe
p-OMe
p-Me
p-Cl
p-Me
H
Ph
H
5f
(p-Cl)Ph
7
Bn
H
5g
(m-Me)Ph
(m-Br)Ph
(m-Br)Ph
8
Ph
H
5h
5i
Ph
9
Et
H
(m-Me)Ph
10
11
12
13
14
Et
H
5j
p -ClPh
Ph
H
5k
With L9 in hand, its catalytic performance was evaluated in the
carbonylative Heck reaction between PhOTf, CO, and styrene
under the standard conditions (Scheme 3). To our delight, 3a
was obtained in 90% yield in this case. Encouraged by this
p-CF3
H
H
5l
Me
Et
Me
Me
5m
5n
H
result, the scope of the reaction was investigated. Phenyl Then we focused on the chemical derivation of Heck-type
triflates bearing both electron-donating and halides groups carbonylative products Na2CO3-prompted [3+2]
3f) with N-
smoothly progressed
3.
afforded the corresponding chalcones in moderate yields (73– cycloaddition of substituted chalcones
88% yields). However, phenyl triflates bearing strong electron benzyl-2-bromo-2-methyl propanamide
withdrawing groups, such as –NO2 and –F, produced poor 3f
3
6
(3c, 3d,
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2
For Pd-catalyzed Intramolecular Carbonylative Heck
reactions, please see: (a) E.-I. Negishi and J. A. Miller, J. Am.
Chem. Soc., 1983, 105, 6761-6763; (b) J. M. Tour and E.-i.
Negishi, J. Am. Chem. Soc., 1985, 107, 8289-8291; (c) E.-i.
in HFIP at room temperature, affording novel and
polysubstituted
γ
-lactams
7
(
7a, 7b, 7c). (Scheme 3)
O
Negishi, G. Wu and J. M. Tour, Tetrahedron Lett., 1988, 29
,
O
Me
Br
OBn
N
6745-6748; (d) E.-i. Negishi and J. M. Tour, Tetrahedron Lett.,
1986, 27, 4869-4872; (e) E.-i. Negishi, S. Ma, J. Amanfu, J. A.
Miller and J. M. Tour, J. Am. Chem. Soc., 1996, 118, 5919-
5931; (f) E.-i. Negishi, S. Ma, T. Mita, T. Sugihara and J. M.
Tour, J. Am. Chem. Soc., 1996, 118, 5904-5918; (g) C. Coperet,
OBn
Me
Me
H
6
N
*
O
Me
Na2CO3 ( 2 eq)
*
R1
HFIP, 25 o
C
O
R2
R1
R2
3f: R1 =p-NO2, R2 = H
3d: R1 = p-Br, R2 = H
3c: R1 = o-OMe, R2 = H
S. Ma and E.-i. Negishi, Angew. Chem., Int. Ed., 1996, 35
2125-2126.
,
7a: R1 = p-NO2, R2 = H; 88% yield; d.r>20:1
7b: R1 = p-Br, R2 = H; 85% yield; d.r>20:1
7c: R1 = o-OMe, R2 = H; 84% yield;d.r>20:1
3
4
(a) A. L. Casalnuovo and J. C. Calabrese, J. Am. Chem. Soc.,
1990, 112, 4324-4330; (b) K. H. Shaughnessy, Chem. Rev.,
2009, 109, 643-710 and references cited therein.
For phosphines with anionic substituents, please see: (a) W.
A. Herrmann, G. P. Albanese, R. B. Manetsberger, P. Lappe
and H. Bahrmann, Angew. Chem., Int. Ed., 1995, 34, 811-813;
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Muxworthy. Tetrahedron Lett., 2000, 41, 4503-4505; (c) L. R.
Scheme 3. [3+2] cycloaddition of substituted chalcones in HFIP (HFIP=1,1,1,3,3,3-
hexafluoro-2-propanol)
In summary, an efficient, hydrophilic and recyclable
methoxypolyethylene glycol grafted s-triazine-based N,P-
ligand for Pd-catalyzed carbonylative Heck coupling reaction
was developed in this study, providing a straightforward,
effective and mild route for the preparation of diverse α,β-
unsaturated ketones. In the presence of Pd(OAc)2 and
hydrophilic ligand L9, diverse 1,4-dicarbonyl esters could also
be obtained in satisfactory yields. Although this catalytic
system could be recycled several runs with slightly decreased
yields, the methoxypolyethylene glycol grafted s-triazine-
based N,P-ligand L9 still proved to be a multifunctional and
useful ligand in homogeneous catalysis and green chemistry.
Moore and K. H. Shaughnessy, Org. Lett., 2004, 6, 225-228;
(d) H. Gulyas, Z. Bascik and J. Bakos, Adv. Synth. Catal., 2006,
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Weferling and W. S. Sheldrick, Angew. Chem., Int. Ed., 1993,
32, 1058-1059.
For phosphines with cationic substituents, please see : (a) R.
T. Smith and M. C. Baird, Inorg. Chim. Acta., 1982, 62, 135-
139; (b) R. Kreiter, K. Gebbink and G. Van Koten,
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6
7
and R. S. Booth, Org. Lett., 2001,
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0
(e) B. Mohr, D. M. Lynn and R. H. Grubbs, Organometallics,
1996, 15, 4317-4325.
For phosphines with neutral hydrophilic substituents, please
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Henry, A. Iourtchenko and D. Sinou, Tetrahedron Lett., 2002,
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see: (a) T. Malmstrom and C. Andersson, J. Mol. Catal. A:
Chem., 2000, 157, 79-82; (b) J. Jiang, Y. Wang, C. Liu, Q. Xiao
and Z. Jin, J. Mol. Catal. A: Chem., 2001, 171, 85-89; (c) R.
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Acknowledgement
This work was supported by the 111 Project (B14041), National
Natural Science Foundation of China (Grants Nos. 21271124,
21272186 and 21371112), Fundamental Funds Research for
the Central Universities (Grant Nos. GK201501005,
GK201302015 and GK201503029), Natural Science Basic
Research Plan in Shaanxi Province of China (Program Nos.
2015JQ2056 and 2017JM2001). This work was also partially
supported by “One Hundred Talented People” of Shaanxi
Province.
Eur. J., 2003,
9, 3228-3234; (e) K. Breitenkamp and T. J.
Emrick, Polym. Sci., Part A: Polym. Sci., 2005, 43, 5715-5721;
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Notes and references
1
For Heck’s pioneering work, please see (a) A. Schoenberg, I.
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8
(b) A. Schoenberg and R. F. Heck, J. Org. Chem., 1974, 39
,
3327-3331; (c) A. Schoenberg and R. F. Heck, J. Am. Chem.
Soc., 1974, 96, 7761-7774; For Pd catalyzed carbonylative
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Johansen, A. T. Lindhardt and T. Skrydstrup, ACS Catal., 2016,
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Graphic Abstract
A Robust Multifunctional Ligand-controlled Palladium-Catalyzed
Carbonylation Reactions in Water
Pei-Sen Gao, Kan Zhang, Ming-Ming Yang, Shan Xu, Hua-Ming Sun, Jin-Lei Zhang, Zi-Wei Gao*,
Wei-Qiang Zhang *, Li-Wen Xu*
O
R2
CO (5 bar)
R1
Pd(OAc)2 (2 mol%)
L9 (10 mol%)
R2
Cs2CO3 (3 eq.)
OTf
water, 95 oC, 20 h
R1
O
OR2
R1
O
COOR2
A
novel and robust methoxypolyethylene glycol (PEG)-modulated s-triazine-based
multifunctional and hydrophilic Schiff base/N,P-ligand L9 was successfully employed in the
Pd-catalyzed Heck-type carbonylative coupling reactions, yielding a variety of chalcone
derivatives and 1,4-dicarbonyl esters in good yields.