Highly Efficient Palladium-Catalyzed Allylic Alkylation of Cyanoacetamides with Controllable and Chemoselective Mono- and Double Substitutions

Article abstract of DOI:10.1002/cctc.201601021

It was found that catalytic allylation of various cyanoacetamides proceeded smoothly and efficiently in environmentally benign PEG-400 (PEG=poly(ethylene glycol)) in the presence of Pd(OAc)₂ and novel triazine-derived multifunctional ligand L1, with which this reaction could afford the structurally diverse mono- and double allylated adducts in good to excellent yields as well as good chemo- and regioselectivity. In addition, this Pd/L1/PEG-400 catalyst system could be recycled for five runs with good yield and high efficiency, which supported the notion that the triazine-containing Schiff base based phosphine ligand could be a multifunctional and reusable ligand encapsulated in PEG-400.

Full text of DOI:10.1002/cctc.201601021

Accepted Article
Title: Highly Efficient Palladium-Catalyzed Allylic Alkylation of
Cyanoacetamides with Controllable and Chemoselective Mono-
and Double- Substitutions
Authors: Li-Wen Xu, Pei-Sen Gao, Ning Li, Jin-Lei Zhang, Zhuang-Li
Zhu, Zi-Wei Gao, Hua-Ming Sun, and Wei-Qiang Zhang
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To be cited as: ChemCatChem 10.1002/cctc.201601021
Link to VoR: http://dx.doi.org/10.1002/cctc.201601021
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10.1002/cctc.201601021
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Highly Efficient Palladium-Catalyzed Allylic Alkylation of
Cyanoacetamides with Controllable and Chemoselective Mono-
and Double- Substitutions
Pei-Sen Gao,[a,b] Ning Li,[a] Jin-Lei Zhang,[a] Zhuang-Li Zhu,[a] Zi-Wei Gao,*[a] Hua-Ming Sun,[a] Wei-
Qiang Zhang,[a] Li-Wen Xu*[a,b]
Dedication ((optional))
Abstract: It was found that catalytic allylation of various
cyanoacetamides proceeded smoothly and efficiently in
environmentally benign PEG-400 (PEG = poly(ethylene glycols)) in
the presence of Pd(OAc)2 and novel triazine-derived multifunctional
ligand L1, in which this reaction could afford the structurally diverse
mono- and double- allylated adducts in good to excellent yields as
well as good chemo- and regio-selectivity. In addition, this
Pd/L1/PEG-400 catalyst system could be recycled five runs with
good yield and high efficiency, which supported the triazine–
agents.[5-8] However, it is recognized as a challenge to use
cyano-containing acetamides (cyanoacetamides) in
environmentally benign and chemoselective allylic alkylation
because of low nucleophilic activity and the stabilized nature of
Pd-NC coordination derived from cyano moiety with palladium
center.
And from the standpoint of green chemistry and industrial
applications of expensive palladium catalysts, the development
of a recyclable and reusable palladium catalyst system that
allows for the highly efficient allylic alkylation is highly desirable.
Exceptionally, the exploring of highly efficient and recyclable
palladium catalyst systems tolerated various functional groups
for this reaction is much valuable.[9] It should be also noted that,
one important and practical aspect of synthetic chemistry toward
green processes is the development of recyclable palladium
catalysts that provide high chemoselectivity and good activity in
various chemical reactions. However, the decrease of catalytic
activity of recovered metal complex-based catalysts was a
containing Schiff base-based phosphine ligand could be
multifunctional and reusable ligand encapsulated in PEG-400.
a
Introduction
Since the pioneering work of Tsuji and Trost,[1] the palladium-
catalyzed allylic alkylations offers one of the most convergent
approaches for the construction of complex molecular
frameworks, and has become a fundamental carbon-carbon
bond-forming reaction in synthetic chemistry.[2] This prestigious
reaction has been developed into many synthetically useful
variants.[3,4] Despite the use of -allyl palladium chemistry for the
construction of γ-lactams via intramolecular allylic alkylation of a
resonance-stabilized carbanion linked with an activated amide
and an allylic acetate has been described extensively by several
groups,[5] a highly efficient intermolecular allylic alkylation of
cyano-activated acetamides is still elusive. Little attention has
been dedicated to finding mild and catalytic chemoselective
approaches for the allylic alkylation of amide- and cyano-
containing functional carbonyl compounds.[6,7] In fact, substituted
cyano-containing carbonyl compounds as well as functional
amides are useful class of building blocks in organic synthesis,
bioactive natural products, drug discovery, and pharmaceutical
common phenomenon
in homogeneous catalysis.[10,11]
Therefore, it is an important topic in terms of the
chemoselectivity and recyclability of palladium catalyst,
environmentally benign process, and efficiency of new catalyst
system as well as adaptability of allylic alkylation chemistry for
the application in industry. Although various reports of catalytic
transformations of cyano-containing carbonyl compounds
exists,[5-8,11] there remains considerable room for development of
green process for allylic alkylation reaction with cyano-
containing carbonyl compounds and improvement in terms of
functional group tolerance, which could enable an
environmentally benign methodology ideal for use in the field of
green chemistry and complex molecule synthesis.[12,13]
Notably, among the recyclable and green solvents,
poly(ethylene glycols) (PEGs) has been attracted much
attentions in homogeneous catalysis and has become one of the
suitable choices as reused solvent due to its non-flammable,
non-toxic, inexpensive and recoverable nature.[14] So far, PEGs
have been successfully employed as reaction media for
palladium-catalyzed carbon-carbon bond-forming reaction.[15-18]
Surprisingly, there is no report on Pd-catalyzed allylic
substitutions in PEGs with a recyclable and efficient manner.
Thus we would like to present our findings on controllable mono-
and double- allylic substitutions using a palladium catalyst, new
triazine-derived ligand, cyano-containing acetamides, simple
allylic acetate, and an environmentally benign PEG-400 media,
[a]
[b]
Mr. P.S. Gao, Miss N. Li, Miss J.L. Zhang, Mr. Z.L. Zhu, Prof. Z.W.
Gao, Dr. H.M. Sun, Prof. Dr. W.Q. Zhang, Prof. Dr. L.W. Xu
Key Laboratory of Applied Surface and Colloid Chemistry, Ministry
of Education (MOE) and School of Chemistry and Chemical
Engineering, Shaanxi Normal University, Xi’an 710062, P. R. China.
E-mail: zwgao@snnu.edu.cn (GZW); liwenxu@snnu.edu.cn (XLW)
Prof. Dr. L.W. Xu
Key Laboratory of Organosilicon Chemistry and Material Technology
of Ministry of Education, Hangzhou Normal University (HZNU), P. R.
China
in which
a
facile preparation of substituted dicarbonyl
E-mail: liwenxu@hznu.edu.cn (XLW)
compounds was finished with excellent chemoselectivities and
controllable mono- and double- allylic substitutions via
Supporting information for this article is given via a link at the end of
the document.((Please delete this text if not appropriate))
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environmentally benign process. In addition, our method
regarded of allylic alkylation of cyano-containing acetamides is
distinguished from earlier reports in terms of new ligands and
recyclability of catalyst systems.
Table 1. Optimization of Pd-catalyzed mono-allylation of cyano-containing
acetamide 1a with allylic acetate 2a[a]
Results and Discussion
For initial tests, we chose 2-cyano-N,N-diphenylacetamide (1a)
and simple allylic acetate (2a) as model substrates for the allylic
alkylation reaction using Pd(OAc)2, DPEPhos, K2CO3 and PEG-
400 at room temperature. Interestingly, in this preliminary check,
only a trace amount of desired product 3a was observed (Table
1, Entry 1). Other commercially available phosphine ligands,
such as XtanPhos and PCy3, could not promote the palladium
catalyzed allylic alkylation to afford the product 3a (Entries 2 and
3, also see Table S1 of ESI). This observation prompted us to
develop novel multifunctional phosphine ligands for the titled
reaction. In addition, the design and synthesis of new ligand with
highly catalytic efficiency and excellent chemoselectivity is
necessary in the catalytic allylation chemistry.
Entry
Ligand
Solvent
Yield of 3a
3a/4a/5a/6a[c]
(%)[b]
1
DPEPhos
PEG-400
PEG-400
PEG-400
PEG-400
PEG-400
PEG-400
PEG-400
PEG-400
PEG-400
H2O
trace
N.D
N.D
71
--
2
XtanPhos
PCy3
L5
--
3
--
H2N
NH2
Cl
N
O
N
O
CHO
N
N
4
75/0/25/0
72/0/28/0
65/0/35/0
98/0/2/0
55/0/45/0
88/4/5/3
--
N
N
PPh2
~Diamine Linker~
Cl
NH
N
Cl
Ph2P
5
L6
72
L1
Multifunctional P-Ligand
Phosphine center
Functional group
recyclable and reused in PEG-400
6
L7
71
7
L1
93
= L1 =
8
L2
22
9
L3
77
H
O
N
N
N
O
10
11
12
13
14
L1
N.D
72
N
NH
Ph2P
L2
N
N
N
N
N
PPh2
O
Cl
L1
DMSO
85/12/5/3
84/0/13/3
85/0/12/3
90/0/10/0
L3
NH
N
L5
DMF
77
N
N
OMe
N
L6
DMAc
77
PPh2
PPh2
CH
N
L7
DCM
77
L4
MeO
N
L5
[a] The reaction conditions: 1a (1 equiv.), 2a (1.5 equiv.), Pd(OAc)2 (3 mol%),
P-ligand (3.3 mol%), K2CO3 (1.5 eq.) and PEG-400 (1 mL) at room
temperature for 4h. [b] Isolated yield. [c] Ratio of 3a:4a:5a:6a was determined
by 1H-NMR analysis of crude mixture.
CH
N
PPh2
N
HC
PPh2
Ph2P HC
N
CH
Ph2P
Then we focused on a modularly synthetic strategy to triazine-
based multifunctional N,P-ligands on the basis of our previous
findings in Schiff base and phosphine ligand chemistry.[20] As
shown in Figure 1, our approach provided a convergent, and
L6
L7
Figure 1. Structures of new ligands L1-L4 and related P-ligands with Schiff
base moiety[19] used in this work. X-ray crystal structure of the ligand L1
(CCDC 1495547).
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10.1002/cctc.201601021
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highly modular means for the construction of rigid and
multifunctional Schiff base containing one phosphorous and five
nitrogen atoms in most cases (Figure 1, L1-L4). The structure of
new ligand L1 was confirmed by X-ray crystallography (CCDC
1495547). Importantly, the multiple heteroatom-containing
ligands L1-L4 presented in this work were derived from the
aromatic diamine and triazine respectively. The phosphorous
atom or -PPh2 can be easily introduced by 2-
diphenylphosphanyl-benzaldehyde (The detailed synthetic
procedures for the synthesis of new ligands L1-L4 were
provided in Supporting Information), in which the linked reaction
is the simple condensation of aldehyde and primary amine to
construct the Schiff base moiety. Notably, we hypothesized that
triazine core would be beneficial to the encapsulation of
palladium catalyst in PEG-400, especially for the ether-
containing triazine-derived ligands L1-L4. To support the
importance of triazine moiety in this work, other simple Schiff
base-based phosphine ligands, for example, ligand L6,[19] were
also used for comparison in the palladium catalyzed allylic
alkylation of cyano-containing acetamide.
With phosphine ligands L1-L4 (Figure 1) in hand, we then test
the performance of these Schiff-base phosphine ligands in the
titled reaction. Notably, the allylic alkylation of cyano-containing
acetamide 1a with allylic acetate 2a is not so simple as imagined
because four possible product could be formed in the presence
of palladium catalyst. Gratifyingly, triazine-linked multifunctional
phosphine ligand L1 could promote the palladium-catalyzed
allylic substitution to afford 93% yield of 3a and exhibited both
excellent chemo- and regio-selectivity, with 98:2 of 3a/5a and
without the observation of double allylated product either 4a or
6a. Unexpectedly, when L2 and L4 bearing a chloride group
around the triazinal core were individually tested in the allylic
alkylation reaction, the yield and chemoselectivity were
significantly decreased obviously, only to give 22% and 58%
yield of 3a respectively (Entries 8 and 9). Interestingly, the
simple phosphine ligand L5-L7 with Schiff base-based afforded
decreased yield of desired product 3a with lower chemo-
selectivity (Entries 4-7). In addition, undesired isomerization
reaction of 3a occurred to give 5a, which was detected based on
1H-NMR analysis of the reaction mixture. Next, solvents were
also tested under identical conditions in the presence of
Pd(OAc)2 and L1. It was found that other solvents, such as
DMSO, DMF, DCM, and DMAc, afforded the moderate yield of
desired 3a and exhibited poor selectivity (Entries 10-14).
Although the high efficiency and good selectivity could be also
achieved in MeCN, THF, and Toluene (Table S3-S5 of ESI),
PEG-400 is still the ideal choice of solvent due to the
environmentally friendly property, inexpensive and recyclability
nature. Then, different bases and Pd-catalysts were tested and
series of experiments were carried out to examine the effect of
various reaction parameters (See Table S2 and Table S6 of ESI
respectively), such as bases, catalyst loading on the yield of the
desired product and the equivalent of substrates, which
supported the optimized reaction conditions provided in Entry 1
of Table 1. Notably, in the absence of triazine-derived phosphine
ligand L1, the reaction did not occur and the starting materials
were recovered completely.
Pd(OAc)2 (3 mol%)
L1 (3.3 mol%)
NR1R2
NC
CN
+
OAc
NR1R2
O
NC
K2CO3 (1.2 eq),
PEG-400, rt
O
1
2a
3
H
N
H
H
N
N
NC
Me
N
NC
NC
O
O
O
O
OMe
3d
90% yield
3b
3c
91%yield
3a
93% yield
92% yield
OMe
H
H
N
H
N
H
N
N
NC
NC
NC
NC
O
O
O
O
3e
90% yield
3g
90% yield
3h
79% yield
Cl
3f
88% yield
H
N
H
N
N
O
N
NC
NC
NC
NC
Cl
O
O
O
Br
3j
3i
3k
90% yield
3j
91% yield
80% yield
77% yield
MeO
Me
O
N
O
CN
CN
O
iPr
N
N
NC
O
NC
tBu
O
3p
65% yield
3m
91% yield
3o
95% yield
Me
3n
93% yield
MeO
Scheme
1.
Palladium-catalyzed
allylic
substitution
of
different
cyanoacetamides with allylic acetate 2a.
Encouraged by above results, we evaluated a series of different
substrates to determine the specificity and scope of substrates
for this Pd/L1 catalyst system. Experimental probing the
substrate scope of mono-substituted allylic alkylation are
summarized in Scheme 1. Both electron-donating group and
halide group on the cyano-containing aromatic amides reacted
with allylic acetate in good to excellent yields (up to 95%). The
different cyano-containind amides bearing either N-aryl or O-aryl
residues on the amide and ester moieties[21] were examined and
showed that there is no significant difference among various
amides. Although yield can be further improved, this method
was found to be effective for cyano-containing ester, affording
the corresponding mono-allylic product 3p in high
regioselectivity with moderate yield. Generally, all these allylic
alkylation reactions give excellent chemoselectivities (3/5 ≥ 98:2).
Notably, the double allylated product 4 was not detected under
the optimized reaction conditions.
It is important to note that there is no report on the diallylation of
cyano-containing carbonyl compounds, and the triazine-derived
ligand -involved palladium catalyst system described here shows
exceptional functional cyano group tolerance and high
chemoselectvities under mild reaction conditions, encompassing
a remarkably wide substrate scope. After establishing the Pd/L1
catalyst system in the mono-allylation of cyano-containing
acetamides, we envisioned that this catalytic system could be
employed in the one-pot double-allylation of cyano-containing
acetamides with simple allylic acetate 2a directly. On the basis
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of the above findings with Pd/L1 system in THF (Table S4 of
ESI), we hypothesized that the double-allylation was
a
13
14
15
16
17
KOtBu
KOtBu
KOtBu
KOtBu
KOtBu
CHCl3
Toluene
H2O
37
thermodynamic process and could be achieved by elevating the
reaction temperature and changing the bases. Initially, we
conducted the reaction of 1b (1 equiv.) and 2a (2.2 equiv.) in
PEG-400 at 70 oC overnight under 3 mol% of Pd(OAc)2, 3.3
mol% of L1, and K2CO3 (2.2 equiv.). To our delight, 25% yield of
double-allylated product 4b was obtained in this case (Table 2,
Entry 1). Then, strong inorganic bases were further tested in this
reaction (Table 2, and Table S8-S9 of ESI). Interestingly, it was
found that KOtBu under the same conditions afforded the
desired product 4b in good yield (Entry 6) and only a trace
amount of mono-allylated product was detected. We also
checked the effect of the solvents on the catalytic performance
of Pd/L1 catalyst in this reaction (Entries 10-17). As shown in
Table 2, it was found that PEG-400 is still the best media for
palladium/L1 –catalyzed double-allylation of 1b with allylic
acetate (2a).
57
N.D
80
THF
MeCN
82
[a] The reaction conditions: 1b (1 equiv.), 2a (2.5 equiv.), Pd(OAc)2 (5
mol%), ligand L1 (5.5 mol%), base (2.2 equiv) and PEG-400 (1 mL) at 70
oC for overnight unless otherwise noted. [b] Isolated yield.
Pd(OAc) (3 mol%)
2
L1 (3.3 mol%)
NR R
1
2
NC
+
NR R
1
2
OAc
t
NC
KO Bu (1.2 eq),
O
o
O
PEG-400, 70
C
Table 2. Optimization of Pd-catalyzed double-allylation of 1b with allylic
acetate (2a).
1
2a
4
H
N
H
N
H
NC
OMe
NC
N
NC
O
O
Me
O
4b
88% yield
4c
86% yield
4a
85% yield
4a
OMe
H
N
H
N
H
N
H
Me
N
NC
Et
NC
Entry[a]
Base
Solvent
Yield (%)[b]
25
NC
NC
O
O
O
O
4e
Me
4d
4f
4g
87% yield
87% yield
83% yield
88% yield
1
K2CO3
Cs2CO3
NaOH
KOH
PEG-400
PEG-400
PEG-400
PEG-400
PEG-400
PEG-400
PEG-400
PEG-400
PEG-400
DMSO
2
37
H
N
H
N
NC
NC
O
O
n
Bu
Cl
3
32
4h
4i
4i
85% yield
74% yiled
4
40
H
N
H
N
NC
NaOtBu
KOtBu
DIPEA
DABCO
DBU
81
NC
5
O
O
Br
4j
71% yield
Cl
4k
4j
72% yield
6
88
OMe
Me
7
trace
trace
7
NC
NC
NC
NH
NC
NH
N
O
N
O
O
O
8
I
OMe
CF
3
Me
4l
69% yield
4m
70% yield
4n
90% yield
4o
92% yield
9
Scheme 2. Pd-catalyzed double-allylation of different cyanoacetamides with
allylic acetate. X-Ray structure of double-allylic products 4a, 4i, and 4j (CCDC:
1497436, 1497437, 1497438). H atom was omitted for clarity. Red-C, dark
blue-N, sky blue- O, and green- Cl.
10
11
12
KOtBu
KOtBu
KOtBu
trace
trace
41
DMF
DCM
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With the optimized conditions in hand (Pd/L1 catalyst system,
KOtBu as base, PEG-400 as solvent, 70 oC), we then studied the
scope of various cyano-containing acetamides and allylic
acetate. As shown in Scheme 2, most of amides afforded the
desired double-allylated products in good to excellent yields (up
to 92%) with excellent chemoselectivity. High reactivity was
consistently observed when secondary amides and tertiary
amides were used as electrophiles. Moreover, the structure of
new products, such as 4a, 4i, and 4j, were confirmed by X-ray
crystallography (Scheme 2).
as –CF3 ,-NO2, -F only undergo the hydrolysis to give the
corresponding phenols, without observation of desired allylic
products.
To check the recyclability of the catalyst Pd(OAc)2/L1 in PEG-
400, the mono-allylation of 2-cyano-N,N-diphenylacetamide was
examined in the presence of 3 mol% of Pd(OAc)2 and 3.3 mol%
of L1. After initial test, the reaction mixture was extracted with
diethyl ether, and the PEG-400 –encapsulated Pd/L1 system
was subjected to a second run by charging with the same
substrates and addition of K2CO3. We were gratified to observe
that the Pd(OAc)2/L1 catalyst system could be immobilized in
PEG-400 phase. As shown in the Table 3, the catalytic system
could be recycled and reused five times with only slightly loss of
activity. The yields of 3a in every runs were 93%, 93%, 91%,
91%, and 88% for 4 h, respectively. We believed that PEG-400
might chelate Pd and good solubility with methyl ether-tagged
triazine linked Schiff base/phosphine ligand, hasten the
formation of recyclable Pd/L1/PEG-400 catalyst system.
In order to understand the reaction mechanism as well as the
detection of activated species involving in the mono-allylation
process, we conducted series of controlled experiments. Initially,
various allylic ethers with different leaving groups were tested.
As described above, allylic acetate 2a could afford the desired
mono-substitution in 93% yield with both good chemoselectivity
(98:2) and regioselectivity. However, when allylic carbonate 2b
or 2c was employed instead of 2a as allylic sources, the yield of
3a was decreased obviously, giving 54% or 47% yield
respectively. The poor chemoselectivity and regioselectivity
were also observed in these cases (Entries 2 and 3 of Table S7).
In addition, vinyl phosphate 2d is not a suitable allylic substrate
in this reaction (Scheme 4).
Pd(OAc) (3 mol%)
2
O
L1 (3.3 mol%)
R
+
O
CN
OAc
O
t
KO Bu (2.2 eq),
R
NC
O
o
1p, R = OMe
1q, R = Me
PEG-400, 70 C, overnight
4p, R = OMe, 68% yield
4q, R = Me, 62% yield
t
1r, R = Bu
O
N
O
N
N
t
4r, R = Bu, 65% yield
N
NH
Ph P
2
Ligand L1 =
Scheme 3. Palladium catalyzed double-allylation of cyanoesters.
Table 3. Recyclability of Pd/L1/PEG-400 for the monoallylic alkylation of 2-
cyano-N,N-diphenylacetamide.
[Pd] (3 mol%)
L1 (3.3 mol%)
NPh2
NC
OAc
NPh2
+
K2CO3 (1.2 eq.)
PEG-400, 4 h, rt
NC
O
2a
1a
O
3a
Pd(OAc)2 (3 mol%)
L1 (3.3 mol%)
NPh2
NC
+
R
NPh2
O
NC
K2CO3 (1.2 eq),
PEG-400, rt
O
1
2
PPh2
N
3
Yield of 3a: 93% (with 2a) > 54% (with 2b) > 47% (with 2c) >0% (with 2d)
NH
O
N
N
O
O
OH
>
>
OAc
>
OCOOMe
OCOOtBu
OP(OEt)2
HO
n PEG-400
O
N
O
2a
2b
2c
2d
tag
Scheme 4. Palladium-catalyzed monoallylation of cyanoacetamide 1a with
various allylic substrates 2a-2d.
Runs
1
2
3
4
5
Then, we conducted several competing experiments between
different cyano-containing carbonyl substrates with allylic
acetate 2a (Scheme 5 and S1-S2, see Supporting Information).
Cyano-containing acetamide bearing ethyl group at the terminals
(1d) appeared to react with 2a much faster than that bearing
chloride group at the terminals (1i), with 5:1 molecular ratio of
the desired product 3d/3i (Scheme 5, equation 1). These results
were consistent with the fact that the yield of mono-allylate
product was influenced by substituted pattern at the phenyl units
in a sequence: electron-donating groups > halide groups. We
Yield (%)
93%
93%
91%
91%
88%
The described reactions could also, in principle, be extended to
a catalytic allylic alkylation of cyanoesters. To further evaluate
the reaction, we next examined the double allylation of
cyanoesters with allylic acetate. As shown in Scheme 3, the use
of cyano-containing ester bearing electron-donating groups at
the phenyl ring as substrates resulted into corresponding
double-allylated products with moderate yields (62-68%).
However, cyano-ester bearing electron-donating groups, such
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also tested the activity of cyanoacetamide 1d with ester 1p. The
high selectivity was obtained with 25:1 molecular ratio of 3d:3p,
suggesting that cyanoacetamide is more reactive to undergo
allylation than that of corresponding cyanoesters.[21] At last, we
monitored the reaction by the ESI-MS and NMR analysis,
including 1H NMR spectroscopy in d3- MeCN (Scheme S3).
Thus on the basis of experimental results and the commonly
accepted mechanism for the Pd-catalyzed allylic alkylation
involves four discrete steps,[22] including metal-allyl coordination,
ionization, nucleophilic addition, and decomplexation, we
proposed the possible mechanism for the palladium–catalyzed
allylic alkylation of activated amides (Scheme 6). As shown in
Scheme 4, the nucleophilic addition of the in-situ formed enolate
to the -allylpalladium complex leads to the formation of an
alkylated products associated with re-generation of the
palladium catalyst. In this mechanistic rationale, the in-situ
formed palladium/L1 complex give a tetra-coordinated Pd(II)
species (I), followed by ligand exchange process to give a
palladium intermediate (II) with allylic acetate (2a). Then with the
assistance of 1,3,5-triazinal core and K2CO3, the intermediates II
underwent oxidation to form Pd/L1 π-allylpalladium intermediate
(III), followed by nucleophilic attack on the allyl terminus,
resulting into reductive elimination of the palladium center to
afford the desired -allylated product.
Cl
O
H
N
CN
2a (1.2 eq.)
NC
N
H
Pd(OAc) (3 mol%)
2
L1 (3.3 mol%)
O
1i
NC
1d
Cl
1i/1d = 1:1
(1)
H
N
3i
K CO (1.2 eq),
2
3
+
PEG-400, r.t
O
H
Et
N
3d/3i = 5:1
NC
O
Et
3d
H
N
H
NC
1d
N
2a (1.2 eq.)
NC
O
Et
Pd(OAc) (3 mol%)
2
O
Et
+
L1 (3.3 mol%)
1d/1p = 1:1
3d
(2)
O
K CO (1.2 eq),
NC
1p
+
2
3
PEG-400, r.t
3d/3p = 25:1
O
n
Bu
O
NC
O
n
Bu
3p
Scheme 5. Competitive monoallylation with allylic acetate 2a between
different cyanoacetamides: The electronic effect of substituents on the aryl
ring of cyanoacetamides.
Scheme 7. Studies on the synthesis of cyanoacetamide derivatives from
allylated cyanoacetamides.
Moreover, with the two types of alkylated cyanoacetamides in
hand, we devoted to the chemoselective transformations of
these structurally diverse allylated cyanoacetamides under
different circumstances, including hydrolysis/esterification of
cyano group and fluorination. As shown in Scheme 7, double-
allylated amide 4d or 4g underwent metathesis under catalytic
amount of Grubbs’ II catalyst in THF leading to novel
cyclopentene derivatives. In addition, it is well-known that
introduction of fluoride atom(s) into a molecule brings out
valuable properties.[23] Accordingly, mono-fluorinated 1,3-
Scheme 6. Possible mechanism for the monoallylation of cyanoacetamide 1a
with allylic acetate 2a.
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[2]
[3]
a) B. M. Trost, T. R. Verhoeven, in Comprehensive Organometallic
Chemistry, W. Bartmann, K. B. Sharpless, Eds, Pergamon Press:
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Catalysts, Wiley-VCH, Singapore, 2011.
dicarbonyl compounds, are widely used in asymmetric synthesis
and construction of biologically active molecules.[24] With the
mono-allylated cyanoacetamide and corresponding allylated
dicarbonyl product in hand , we obtained the desired fluorinated
carbonyl compound
9 in good yield under new reaction
conditions (Cp2TiCl2 as catalyst). In addition, further efforts to
develop new synthetic methods for the catalytic application of
allylated cyanoacetamides, and on the basis of above findings
descried in this work, the development of chiral triazine-derived
N,P-ligand for recyclable Pd-catalyzed enatioselective allylation
are underway in our laboratory.
For recent examples, see: a) h) A. Harada, Y. Makida, T. Sato, H.
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Conclusions
In summary, an efficient and recyclable triazine-linked N,P-
ligand for Pd-catalyzed controllable allylation reaction has been
developed in this work, providing a direct and effective route to a
variety of substituted cyanoacetamides, in which the resulting
homogenous palladium catalyst and liquid/liquid separation also
featured with facile recovery and reuse, easy preparation, and
high selectivity. In the presence of Pd(OAc)2 and novel triazine-
derived ligand L1, catalytic allylation of various kinds of cyano-
containing acetamides proceeded smoothly and efficiently with
the assistance of base in environmentally benign PEG-400 to
afford the desired mono- and double- substitutes in good to
excellent yields as well as good chemo- and regio-selectivity.
This catalytic system could be recycled five runs with slightly
loss of catalytic activity. Thus the triazine–containing Schiff
base-based phosphine ligand was proved to a multifunctional
and important ligand encapsulated in PEG-400, and in other
word, environmentally benign PEG-400 could be catalyst
support in homogeneous reaction and heterogeneous
separation, in which the combinational use of triazine–derived
phosphine ligand and palladium catalyst combined with PEG-
400 was also shown to be recyclable up to 5 times with good
yield and efficiency. Studies are ongoing to gain insight into the
catalytic relationship between structures and properties of the
triazine-derived phosphine ligand and expanding its further
applications to green chemistry and asymmetric catalysis.
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Acknowledgements ((optional))
This project was supported by the National Natural Science
Founder of China (No. 21173064, 21371112, 21446014, and
21472031). This work is also supported partially by Fundamental
Research Funds for the Central Universities (GK201501005,
201503029). This work is also supported partially by the
Program of “One Hundred Talented People” of Shaanxi Province.
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Keywords: Palladium • Cyanoacetamide • Triazine • Phosphine
ligand • Allylic substitution
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…
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Entry for the Table of Contents (Please choose one layout)
Layout 1:
FULL PAPER
Multifunctional Triazine: A triazine-
modified new phosphine ligand for
Pei-Sen Gao, Ning Li, Jin-Lei Zhang,
Zhuang-Li Zhu, Zi-Wei Gao,* Hua-Ming
Sun, Wei-Qiang Zhang, Li-Wen Xu*
CN
CONR R
Pd/L1
K CO , RT
CONR R
NC
1
2
palladium catalyzed allylic alkylation of
various cyanoacetamides with simple
allylic acetate is developed, which
greatly promotes controllable mono-
allylation and double-allylation of
cyanoacetamides in environmentally
benign and recyclable PEG-400 (PEG
= poly(ethylene glycols)).
2
3
1
2
PEG-400
Pd/L1
Page No. – Page No.
O
N
t-BuOK
o
70
C
Highly Efficient Palladium-Catalyzed
Allylic Alkylation of Cyanoacetamides
with Controllable and
Chemoselective Mono- and Double-
Substitutions
N
NH
N
L1 =
PEG-400
N
O
Ph P
2
CN
CONR R
New Ligand
1
2
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