Selective palladium-catalyzed aminocarbonylation of 1,3-dienes: Atom-efficient synthesis of β,γ-unsaturated amides

Article abstract of DOI:10.1021/ja507530f

Carbonylation reactions constitute important methodologies for the synthesis of all kinds of carboxylic acid derivatives. The development of novel and efficient catalysts for these transformations is of interest for both academic and industrial research. Here, the first palladium-based catalyst system for the aminocarbonylation of 1,3-dienes is described. This atom-efficient transformation proceeds under additive-free conditions and provides straightforward access to a variety of β,γ-unsaturated amides in good to excellent yields, often with high selectivities.

Full text of DOI:10.1021/ja507530f

Article
pubs.acs.org/JACS
Selective Palladium-Catalyzed Aminocarbonylation of 1,3-Dienes:
Atom-Efficient Synthesis of β,γ-Unsaturated Amides
Xianjie Fang,† Haoquan Li,† Ralf Jackstell, and Matthias Beller*
Leibniz-Institut fur Katalyse e.V., an der Universitat Rostock, Albert-Einstein-Str. 29a, 18059 Rostock, Germany
̈
̈
S
* Supporting Information
ABSTRACT: Carbonylation reactions constitute important method-
ologies for the synthesis of all kinds of carboxylic acid derivatives. The
development of novel and efficient catalysts for these transformations
is of interest for both academic and industrial research. Here, the
first palladium-based catalyst system for the aminocarbonylation of
1,3-dienes is described. This atom-efficient transformation proceeds
under additive-free conditions and provides straightforward access
to a variety of β,γ-unsaturated amides in good to excellent yields, often
with high selectivities.
Scheme 1. Synthesis of β,γ-Unsaturated Amides via
Carbonylation Reactions
INTRODUCTION
■
The atom-economic synthesis of amides continues to be one
of the major challenges in synthetic organic chemistry.1 The
amide bond is the key backbone of all natural peptides in
biological systems and is also an important functional group in
organic building blocks and industrial chemicals.2 Traditionally,
amides are synthesized by reactions of carboxylic acids and their
derivatives with amines,3 which suffers from harsh conditions.
In addition, large amounts of side products are often produced.
In this respect, the development of more efficient catalytic
methodologies is still highly important. For example, in recent
years, the palladium-catalyzed aminocarbonylation of aryl
halides,4 alkynes,5 and alkenes6 has become a powerful tool
for the synthesis of aromatic amides, α,β-unsaturated amides,
and aliphatic amides, respectively.
On the basis of our long-standing interest in transition-metal-
catalyzed carbonylation reactions,4a we recently became
interested in the carbonylation of allyl derivatives to give the
corresponding homoallylic compounds, which are synthetically
important but not easily accessible.7 In the past, effective
carbonylation methods for the reaction of allylic carbonates,8
acetates,9 chlorides,10 amines,11 ethers,12 phosphates,9b,e,13 and
alcohols14 to form β,γ-unsaturated esters have been developed.
However, there are few examples known that allow the
synthesis of related β,γ-unsaturated amides via carbonylation
(Scheme 1).8a,11,15
A major problem for any aminocarbonylation methodology
is the competing direct amination of the substrate. In fact,
such aminations of allyl-X compounds should proceed faster than
carbonylations. Moreover, a general drawback of these reactions
is the stoichiometric generation of byproducts (e.g., salts). Alter-
natively, β,γ-unsaturated carboxylic acid derivatives might also be
synthesized by carbonylation of 1,3-dienes. Despite the inherent
advantage of this atom-economic green route (100% atom-
efficient route), the carbonylation of 1,3-dienes has scarcely
been explored in academic laboratories.16 Compared to the
well-studied alkoxycarbonylation of 1,3-dienes,17 to the best
of our knowledge comparable aminocarbonylation reactions to
β,γ-unsaturated amides have not yet been reported (Scheme 1).
On the basis of our previous work on the direct hydro-
amination of 1,3-dienes,18 herein we describe the first general
catalyst system for the direct aminocarbonylation of 1,3-dienes.
Applying a variety of aromatic amines leads to β,γ-unsaturated
amides in good yields and selectivities under neutral conditions.
RESULTS AND DISCUSSION
■
Initially, we investigated the aminocarbonylation of isoprene
(1a) with aniline (2a) as a model reaction in the presence
of [Pd(COD)Cl2] and different phosphine ligands L1−L15
(Scheme 2). In general, we observed two kinds of carbonylated
products: the 1:1 adduct 3aa and the 2:1 adduct 4aa. In both
cases, different regioisomers can be formed. Notably, a preferential
Received: August 19, 2014
© XXXX American Chemical Society
A
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Journal of the American Chemical Society
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Indeed, ring-closing metathesis of 4ba occurred smoothly using
Grubbs II catalyst to give 1-phenyl-1,6-dihydropyridin-2(3H)-
one 5 in 65% yield (eq 2).
Scheme 2. Influence of the Ligand on the Palladium-
Catalyzed Aminocarbonylation of Isoprene (1a) with
a
Aniline (2a)
In order to improve the methodology further, we evaluated
the influence of critical reaction parameters (e.g., palladium pre-
cursor, catalyst loading, temperature, CO pressure) for the
model reaction using L14 as the ligand of choice. As shown in
Table 1, using typical palladium precursors such as Pd(OAc)2,
Table 1. Investigation of Reaction Conditions for Palladium-
Catalyzed Aminocarbonylation of Isoprene (1a) with Aniline
a
(2a)
b
c
entry
[Pd]
temp. (°C)
yield (%)
sel.
a
Reaction conditions: 1a (1.0 mmol), 2a (1.0 mmol), [Pd(COD)Cl2]
1
2
3
4
Pd(COD)Cl2
Pd(OAc)2
Pd(acac)2
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
80
80
0
84:16
(2.5 mol %), monodentate ligand (10.0 mol %), bidentate ligand
(5.0 mol %), CO (50 bar), toluene (2 mL), 100 °C, 20 h; yield and the
ratios of isomers were determined by GC analysis. Y, yield; S, 3aa/3aa′
ratio.
0
PdCl2
89
19
0
84:16
>99:1
d
5
PdCl2
6
Pd(dba)2
e
7
Pd(dba)2
89
0
92:8
attack at the sterically less hindered position is observed.
Nevertheless, minor amounts of 3aa′ are also formed (for details,
see Supporting Information).
f
8
g
Pd(dba)2
9
Pd(dba)2
0
h
10
Pd(dba)2
61
77
84
70
87
64
>99
57
78
95
78
>99
>99
79
94:6
95:5
Unfortunately, the application of monodentate ligands L2
and L3 gave none of the desired product 3aa. However, to our
delight, L1 and cataCXium ligands19 L4−L6 provided desired
product 3aa in moderate to good yield. Further investiga-
tions showed that selected commercially available bidentate
ligands L7−L11 exhibited no activity in the formation of 3aa.
However, when Xantphos (L12) was used, desired product 3aa
is obtained in 44% yield. In addition, significant amounts of the
2:1 adduct 4aa are formed (yield, 28%). Next, some 1,2-bis-
(phosphinomethyl)benzene ligands with different steric proper-
ties were tested, L13−L15. BuPox20 (L14) was identified as
the most promising ligand, and the reaction afforded desired
product 3aa in 80% yield with good selectivity.
In the presence of Xantphos (L12) as ligand, significant
amounts of the 2:1 adduct 4aa were obtained. Apparently, the
yield of 4aa is strongly affected by the molar ratio of 1a to 2a.
Indeed, as the molar ratio of 1a to 2a increased to 5:1, the iso-
lated yield of 4aa increased to 85% (eq 1). From an industrial
point of view, it is interesting that 1,3-butadiene (1b) furnished
the corresponding product 4ba in excellent yield at low catalyst
loading (eq 2). Considering the 1,7-diene structural motif,
product 4 provides the possibility of further transformations.
i
11
Pd(dba)2
12
13
14
15
16
Pd(CH3CN)2Cl2
Pd(PhCN)2Cl2
[Pd(cinnamyl)Cl]2
[Pd(allyl)Cl]2
Pd(TFA)2
Pd(TFA)2
Pd(TFA)2
Pd(TFA)2
Pd(TFA)2
Pd(TFA)2
Pd(TFA)2
Pd(TFA)2
87:13
88:12
93:7
94:6
88:12
92:8
j
17
k
18
91:9
l
19
88:12
88:12
95:5
m
20
21
22
23
60
97:3
>99:1
40
a
Reaction conditions: 1a (1.0 mmol), 2a (1.0 mmol), [Pd] (2.5 mol %),
L14 (5.0 mol %), toluene (2 mL), CO (50 bar), 20 h. Yield
determined by GC analysis. Sel. = 3aa/3aa′ ratio; the ratio of isomers
was determined by GC analysis. 3 Å molecular sieve (200 mg). TFA
(10 mol %). HOAc (10 mol %). H3PO4 (10 mol %). Camphor-
sulfonic acid (10 mol %). p-TsOH·H2O (10 mol %). [Pd] (1.5 mol %),
L14 (3.0 mol %). [Pd] (1.5 mol %), L14 (3.0 mol %), TFA (10 mol %).
CO (40 bar). CO (20 bar).
b
c
d
e
f
g
h
i
j
k
l
m
B
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Journal of the American Chemical Society
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Pd(acac)2, and Pd(dba)2 under the standard reaction condi-
tions, no conversion was observed (Table 1, entries 2, 3, and 6).
However, using Pd(dba)2 in the presence of 10 mol % of either
trifluoroacetic acid, camphersulfonic acid, or p-toluenesulfonic
acid gave the desired product in 61−89% yield (Table 1,
entries 7, 10, and 11). Notably, the use of weaker acids such
as acetic acid and phosphoric acid gave no product (Table 1,
entries 8 and 9). Apparently, a strong acid is required to generate
the catalytically active palladium species (see mechanistic
discussion below). Interestingly, the addition of molecular sieves
impedes the reaction, and the product yield is decreased from 89
to only 19% (Table 1, entries 4 and 5). Without molecular sieves,
the use of other palladium chloride precursors resulted in the
formation of desired product 3aa in 64−89% yield with good
selectivity (Table 1, entries 1, 4, and 12−15). To our delight,
quantitative GC yield of desired amide 3aa was obtained when
Pd(TFA)2 was used as the catalyst precursor (Table 1, entry 16).
Lowering the catalyst loading revealed an optimal loading of
2.5 mol % of [Pd] (Table 1, entry 17). However, at low catalyst
loading, the addition of trifluoroacetic acid also improved the
conversion and restored the catalyst activity (Table 1, entry 18).
The yield of desired amide 3aa decreased when lowering the CO
pressure (Table 1, entries 19 and 20). Interestingly, lowering the
reaction temperature to 80 or 60 °C also resulted in full conversion
and excellent chemo- and regioselectivity. Here, the regioselectivity
for 3aa increased to 97:3 (Table 1, entries 21 and 22).
Scheme 3. Palladium-Catalyzed Aminocarbonylation of
Isoprene (1a) with Aromatic Amines (2)
a
With optimized reaction conditions established (Table 1,
entry 22), we examined the scope of this novel aminocarbonylation
process with respect to amines (Scheme 3). A variety of aromatic
amines with electron-neutral, electron-deficient, and electron-rich
substituents led to the corresponding carbonylative products in
good yields and selectivities. Functional groups including reactive
halide (3ad and 3ah), nitrile (3aj), ketone (3ak), and ester (3al)
groups, which provide useful handles for further synthetic
transformations, are well-tolerated. 2i, as an example of a bulky
substrate, was smoothly transformed to the corresponding
β,γ-unsaturated amide (3ai) in good yield. Interestingly, hetero-
aromatic amines (3am and 3an) proved to be efficient coupling
partners and gave the corresponding amides in decent yields with
good selectivities. Even secondary aromatic amines (2o and 2p)
underwent this transformation and afforded the desired products
in moderate to good yields (3ao and 3ap). Considering the
importance of diamides, which are widely applied for agrochemicals
and used in the polymer industry, we tested the dicarbonylation
of phenylenediamines. As shown in Scheme 3, the reactions of
isoprene 1a with m-phenylenediamine 2q and p-phenylenediamine
2r gave the desired diamides, again in good yields and selectivities
(3aq and 3ar). Unfortunately, no conversion at all was observed
when benzylic amine or n-butylamine was used as coupling partner.
Apparently, in the presence of these more basic amines, the catalyst
activity disappeared.
Next, we evaluated the scope of 1,3-dienes using aniline 2a
as a standard coupling partner (Table 2). Phenyl-substituted
1,3-diene 1c furnished the corresponding desired product in
high yield with excellent regioselectivity, albeit in low stereo-
selectivity (Table 2, entry 2). Furthermore, sterically crowded
1,3-diene 1d was smoothly transformed to the correspond-
ing β,γ-unsaturated amide with excellent selectivity (Table 2,
entry 3). The cyclic 1,3-diene 1e was also efficiently transformed
to the desired β,γ-unsaturated amide (Table 2, entry 4). From
a synthetic point of view, the synthesis of functionalized
β,γ-unsaturated amides from functionalized 1,3-dienes is important,
which is reflected in products 3fa and 3ga, which are obtained
a
Reaction conditions: 1a (1.0 mmol), 2 (1.0 mmol), [Pd(TFA)2]
(2.5 mol %), L14 (5.0 mol %), CO (50 bar), toluene (2 mL), (3ab−
3ae: 60 °C; 3af and 3am: 80 °C; others: 100 °C), 20 h; isolated yield;
the ratio of isomers was determined by GC analysis; in the cases of
3aq and 3ar, a slight excess of 1a (2.1 mmol) was used.
in a straightforward manner using our protocol (Table 2,
entries 5 and 6).
On the basis of previous work on carbonylation of allylic
amines15 and alkoxycarbonylation of allylic alcohols,14f we initially
thought that this transformation proceeds via a sequential C−N
coupling/carbonylation reactions (eq 3). However, the correspond-
ing allylamine 6aa was not observed in the reaction mixture. In
agreement with this observation, no carbonylation of the syn-
thesized allylamine 6aa took place under the standard conditions
(eq 4). Hence, a sequential C−N coupling/carbonylation pathway
seems unlikely in the present reaction process. Although the
detailed mechanism of the palladium-catalyzed aminocarbonylation
of 1,3-dienes is not clear, we suggest the following catalytic cycle
based on our preliminary observations17q and previous work on
aminocarbonylation of olefins6f,g (Scheme 4).
Initially, the catalytic cycle should start from the cationic
palladium hydride species A. Formation of A proceeds in situ
C
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Journal of the American Chemical Society
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Finally, it should be noted that this novel procedure for the
preparation of all kinds of β,γ-unsaturated amides also provides
convenient access to important heterocyclic compounds.
For example, intramolecular hydroamination of 3aa occurred
smoothly under acidic conditions to give γ-lactam 7 in good
yield (Scheme 5a). In addition, substituted benzoxazoles are
Table 2. Palladium-Catalyzed Aminocarbonylation
of 1,3-Dienes (1) with Aniline (2a)
a
Scheme 5. Synthetic Applications
easily available. This is exemplified by the reaction of 3ah to 8
via a Cu-catalyzed C−O coupling reaction21 (Scheme 5b).
Interestingly, 2-allyl quinazolinone 9 was directly produced
using 2-aminobenzamide 2s as the coupling partner. This one-pot
transformation proceeds by a sequential aminocarbonylation/
condensation pathway (Scheme 5c).
a
Reaction conditions: 1 (1.0 mmol), 2a (1.0 mmol), [Pd(TFA)2]
(2.5 mol %), L14 (5.0 mol %), CO (50 bar), toluene (2 mL), 60 °C,
20 h; isolated yield; the ratio of isomers was determined by GC analysis.
b
c
1d (2.0 mmol), 100 °C. 1e (5.0 mmol), [Pd(COD)Cl2] (2.5 mol %),
CONCLUSIONS
■
L12 (5.0 mol %), 100 °C.
In summary, we developed the first general aminocarbonylation
reactions of 1,3-dienes. In the presence of different palladium
phosphine complexes, carbonylation (1:1 adduct) or a selective
hydroamination−carbonylation sequence (2:1 adduct) was
observed. Using different aromatic amines, a variety of syn-
thetically useful β,γ-unsaturated amides are produced in good to
excellent yields. Combining this procedure with established
functionalizations allows for an efficient preparation of various
heterocyclic compounds. The high atom economy and additive-
free reaction conditions make this protocol attractive for syn-
thetic applications, and we believe it will complement the current
methodologies for carbonylations in organic synthesis.
Scheme 4. Proposed Catalytic Cycle
ASSOCIATED CONTENT
* Supporting Information
Experimental details and characterization data. This material is
available free of charge via the Internet at http://pubs.acs.org.
■
S
by reaction of palladium(II) trifluoroacetate and aniline in
the presence of the ligand. Notably, no formation of the
corresponding hydride is observed at room temperature.
However, heating this mixture at 60 °C for 6 h led to the
formation of the respective hydride (for details, see the
Supporting Information). In agreement with previous inves-
tigations on 1,3-diene amination, insertion of isoprene into the
H-palladium bond of the active cationic palladium hydride
species A will lead to π-allyl-Pd complex B′.18a,b Then, CO
addition and insertion to give the corresponding acyl palladium
complex C takes place. Finally, aminolysis of intermediate C
leads to the desired product and regenerates the palladium
hydride species A. With respect to the formation of the active
catalyst, it should be noted that catalysis does not proceed at
room temperature.
AUTHOR INFORMATION
Corresponding Author
Matthias.Beller@catalysis.de
■
Author Contributions
†X.F. and H.L. contributed equally to this work.
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
This work was funded by the BMBF (Germany) and the State
of Mecklenburg-Vorpommern. We thank Dr. Wolfgang
Baumann, Dr. Christine Fischer, Susann Buchholz, and Susanne
Schareina for their technical and analytical support.
D
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Journal of the American Chemical Society
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