Palladium-Catalyzed Aminocarbonylation of Allylic Alcohols

Article abstract of DOI:10.1002/chem.201601260

A benign and efficient palladium-catalyzed aminocarbonylation reaction of allylic alcohols is presented. The generality of this novel process is demonstrated by the synthesis of β,γ-unsaturated amides including aliphatic, cinnamyl, and terpene derivatives. The choice of ligand is crucial for optimal carbonylation processes: Whereas in most cases the combination of PdCl₂with Xantphos (L6) gave best results, sterically hindered substrates performed better in the presence of simple triphenylphosphine (L10), and primary anilines gave the best results using cataCXium PCy (L8). The reactivity of the respective catalyst system is significantly enhanced by addition of small amounts of water. Mechanistic studies and control experiments revealed a tandem allylic alcohol amination/C?N bond carbonylation reaction sequence.

Full text of DOI:10.1002/chem.201601260

DOI: 10.1002/chem.201601260
Full Paper
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Palladium Catalysis
Palladium-Catalyzed Aminocarbonylation of Allylic Alcohols
Haoquan Li, Helfried Neumann, and Matthias Beller*[a]
Abstract: A benign and efficient palladium-catalyzed amino-
carbonylation reaction of allylic alcohols is presented. The
generality of this novel process is demonstrated by the syn-
thesis of b,g-unsaturated amides including aliphatic, cinnam-
yl, and terpene derivatives. The choice of ligand is crucial for
optimal carbonylation processes: Whereas in most cases the
combination of PdCl2 with Xantphos (L6) gave best results,
sterically hindered substrates performed better in the pres-
ence of simple triphenylphosphine (L10), and primary ani-
lines gave the best results using cataCXiumꢀ PCy (L8). The
reactivity of the respective catalyst system is significantly en-
hanced by addition of small amounts of water. Mechanistic
studies and control experiments revealed a tandem allylic al-
cohol amination/CÀN bond carbonylation reaction se-
quence.
Introduction
bility of 1,3-dienes constitute major limitations and thus
prompted us to look for more practical and general methodol-
ogies.
Allylic alcohols represent sustainable and versatile building
blocks in organic synthesis.[1] Among the various allylic sub-
strates, allylic alcohols are the most common and easily ac-
cessed from renewable resources and bulk chemicals. In fact,
many of these substrates are commercially available or can be
conveniently synthesized by numerous methodologies.[2] Fur-
thermore, naturally occurring terpenes such as phytol, geraniol,
nerol, farnesol, etc., are broadly used in the fragrance industry
and have also found various applications in organic synthesis.
For example, the industrial manufacturing of vitamin E and vi-
tamin K1 are based on allylic alcohols.[3]
Due to its specialized structure, investigations for novel
transformations of allylic alcohols have attracted significant at-
tention from both academic and industrial researchers.[4] In this
respect, carbonylation reactions of allylic substrates constitute
versatile tools for the synthesis of b,g-unsaturated carboxylic
derivatives using abundant CO.[5] More specifically, b,g-unsatu-
rated amides are highly useful synthetic intermediates in or-
ganic synthesis, and are typically synthesized from the corre-
sponding activated allylic compounds by cyanation/hydration
reactions,[6] or alternatively, from a,b-unsaturated acid chlorides
by the Arndt–Eistert reaction and subsequent amidation.[7] Re-
cently, we reported an atom-economic aminocarbonylation re-
action of dienes using a palladium/1,2-bis(di-tert-butyl-phos-
phinomethyl)benzene (dtbpx) catalyst system to give b,g-unsa-
turated amides (Scheme 1).[8] Nevertheless, the instability of
most dienes, the gaseous nature of butadiene, and the availa-
Scheme 1. Synthesis of b,g-unsaturated amides: comparison of previous and
current work.
Compared to the direct functionalization of allylic alcohols,
the palladium-catalyzed carbonylation of activated allylic com-
pounds such as allyl halides,[9] allyl carbonates,[10] phospho-
nates,[11] and carbamates[12] have been known since the
1990s.[13] In all these procedures, a significant amount of waste
is inevitably generated not only during the prefunctionalization
step, but also during the reaction process. On the other hand,
palladium-catalyzed carbonylations of allylamines[13b,14] have
also been studied, but suffer from the limited availability of
the starting materials (Scheme 1). In comparison, the direct
aminocarbonylation of allylic alcohols constitutes an ideal
choice regarding availability and stability. Such carbonylations
are challenging due to the poor leaving group ability of the
hydroxyl group.[15] Hence, for direct use of allylic alcohols in
carbonylation reactions, acidic additives such as Lewis acids,[16]
[a] H. Li, Dr. H. Neumann, Prof. Dr. M. Beller
Leibniz-Institut fꢀr Katalyse e. V. an der Universitꢁt Rostock (LIKAT Rostock)
Albert-Einstein-Str. 29a, Rostock, 18059 (Germany)
E-mail: Matthias.Beller@catalysis.de
Supporting information and the ORCID identification number(s) for the au-
thor(s) of this article can be found under http://dx.doi.org/10.1002/
chem.201601260.
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[18]
Brønsted acid,[17] or CO2 are essential. Unfortunately, these
promotors are often deactivated in the presence of basic
amines, such as those used in aminocarbonylation. In continu-
ation of our long-standing interest in carbonylation reactions,
we report here a palladium-catalyzed aminocarbonylation of
allylic alcohols for the first time.[19]
Results and Discussion
At the beginning of our study, the carbonylation of cinnamyl
alcohol (1a, 1 mmol) with N-ethylaniline (2a, 1 mmol) was
chosen as the model reaction (Scheme 2). In the presence of
PdCl2 (1 mol%) as the catalyst precursor, 17 different phos-
phine ligands (4 mol% for monodentate ligands and 2 mol%
for bidentate ligands) were tested without any co-catalyst (see
Scheme 2). Applying commercially bidentate ligands such as
dppb L1 (bite angle 948), dppf L2 (bite angle 998), DPEphos
L3 (bite angle 1048; DPEphos=bis-[2-(diphenylphosphino)phe-
nyl]ether)), and dtbpx L4, all of which have been proven to
promote a variety of carbonylation reactions, only low yields
(15–40%) of the desired product 3aa were obtained. In addi-
tion, with BINAP L5 (bite angle 938), only 1% of the product
could be observed.[20] To our delight, in the presence of Xant-
phos L6 (bite angle 1088), a good yield of 75% was obtained.
From these results, we conclude that a larger bite angle seems
to be beneficial for this reaction.[21] Next, N-phenylpyrrole-type
ligands L7–L9 were tested considering their activity in a variety
of coupling reactions.[22] Among these ligands, the cyclohexyl-
substituted derivative L8 (cataCXiumꢀ PCy) gave the best
result (65% yield). As expected, a variety of standard mono-
dentate ligands (L11–L17) gave no or low conversion. Howev-
er, to our delight, even simple and inexpensive PPh3 L10 gave
a very good result (73% yield), although undesired palladium
black is observed after the reaction. Based on all these results,
the commercially available ligand Xantphos L6 was finally
chosen for the following studies.
Scheme 2. Palladium-catalyzed aminocarbonylation of allylic alcohol: ligand
screening. Reaction conditions: 1a (1 mmol), 2a (1 mmol), ligand (L1–L6
2 mol%, L7–L17 4 mol%), toluene (2 mL), CO (40 bar), 1008C, 24 h; yield de-
termined by GC analysis with isooctane as the internal standard.
al control experiments were conducted (Tables 2 and 3). Under
CO atmosphere, using
a halide-free palladium catalyst
(Pd2(dba)3 as the precursor; dba=dibenzylideneacetone), and
Xantphos as the ligand in the presence of water as the addi-
tive, 31% of 3aa' was observed as the main product, and no
carbonylation to 3aa occurred (Table 2, entry 1). However,
using the same catalyst and adding 5 mol% of HCl, 77% yield
of amide 3aa was observed (entry 2). Interestingly, the addi-
tion of a catalytic amount of allyl chloride (0.5 mol%) also
leads to a good yield of 3aa, which is explained by the forma-
tion of catalytically active allyl-palladium species through oxi-
dative addition. In contrast, adding 10 mol% of NaOH into the
reaction mixture, 3aa' and 3aa were not observed (entry 4).
All these control experiments clearly demonstrate that the
To improve the reactivity of the catalyst system,
we investigated the additive effect. For example,
Table 1. Palladium-catalyzed aminocarbonylation of allylic alcohol: Influence of additi-
when decreasing the catalyst loading to 0.5 mol%,
only 19% yield of 3aa was observed (Table 1, en-
tries 2–3), with the amination product 3aa' as
a major byproduct. Despite the presence of the
amine, the addition of a catalytic amount of trifluoro-
acetic acid (TFA), methanesulfonic acid (MSA), or hy-
drochloric acid (HCl) improved the yield significantly
in each case (entries 4–6, respectively). More surpris-
ingly, when we added water (10 mL), which is a side
product during the reaction, an improved yield was
also obtained (80%, entry 7). Furthermore, fine
tuning the amount of 1a to 1.5 equiv led to quantita-
tive yield of the desired amide (entry 8). Even with
0.25 mol% palladium loading, an excellent yield was
obtained after 48 h (92% yield, entries 9 and 10).
However, further decreasing the catalyst loading to
0.1 mol% gave only traces of 3aa.
ves.[a]
Entry
Pd [mol%]
Ligand [mol%]
Additive
Yield 3aa [%]
1
2
3
4
5
6
7
8
9
PdCl2 (1)
PdCl2 (1)
L6 (2)
L6 (1.5)
–
–
–
75
75
19
75
84
87
80
95[b]
25[b]
92[b,c]
trace[b,c]
PdCl2 (0.5)
PdCl2 (0.5)
PdCl2 (0.5)
PdCl2 (0.5)
PdCl2 (0.5)
PdCl2 (0.5)
PdCl2 (0.25)
L6 (0.75)
L6 (0.75)
L6 (0.75)
L6 (0.75)
L6 (0.75)
L6 (0.75)
L6 (0.375)
TFA (3 mol%)
MSA (3 mol%)
HCl (3 mol%)
H2O (10 mL)
H2O (10 mL)
H2O (10 mL)
10
PdCl2 (0.1)
L6 (0.15)
H2O (10 mL)
[a] General conditions: 1a (1 mmol), 2a(1 mmol), PdCl2, L6, toluene (2 mL), 1008C,
24 h, CO (40 bar). [b] 1a (1.5 mmol). [c] 48 h.
To gain more insight into the mechanism of this
aminocarbonylation reaction of allylic alcohols, sever-
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Table 2. Palladium-catalyzed aminocarbonylation of cinnamyl alcohol 1a:
Control experiments.[a]
Table 3. Palladium-catalyzed aminocarbonylation of 3aa'.[a]
Entry
Additive
3aa [%][b]
Entry
Pd
CO
[bar]
Additive
3aa'
[%]
3aa
[%]
1
2
3
None
HCl (5 mol%)
HCl (5 mol%), H2O (10 mL)
11
25
93
1
2
3
Pd2(dba)3
Pd2(dba)3
Pd2(dba)3
40
40
40
H2O (10 mL)
31
0
0
0
77
80
HCl (5 mol%)
allyl chloride (0.5 mol%)
H2O (10 mL)
NaOH (10 mol%)
None
H2O (10 mL)
HCl (5 mol%)
H2O (10 mL)
[a] Reaction conditions: 3aa' (1 mmol), Pd2(dba)3 (0.0025 mmol,
0.25 mol%), L6 (0.0075 mmol, 0.75 mol%), CO (40 bar), 1008C, 24 h;
[b] Yield determined by GC with isooctane as an internal standard.
4
5
6
7
8
9
PdCl2
40
–
–
–
–
0
15
10
64
90
0
0
–
–
–
–
–
Pd2(dba)3
Pd2(dba)3
Pd2(dba)3
PdCl2
3aa seemed to be accelerated probably due to the decrease
of 2a concentration and also the increase of concentration of
3aa'. Together, the formation and consumption of 3aa'
reached an equilibrium and stayed still for around 200 min at
approximately 40% yield. Then, the concentration of 3aa'
started to decrease along with an increase in yield of 3aa.
PdCl2
–
Et2NH (1 equiv)
[a] Reaction conditions: 1a (1 mmol), 2a (1 mmol), [Pd] (0.005 mmol,
0.5 mol%), L6 (0.0075 mmol, 0.75 mol%), CO (40 bar), 1008C, 24 h.
presence of halide or acid is crucial for the promotion of the
carbonylation process.
To clarify the role of the halide additive further, reaction of
1a with 2a was performed in the absence of CO atmosphere
(Table 2, entries 5–9). Without any additive, only 15% of 3aa'
was formed by palladium-catalyzed allylic substitution reaction
(entry 5). A slightly lower yield of 3aa' was also observed in
the presence of additional water (entry 6). However, addition
of 5 mol% of HCl (in Et2O solution) significantly increased the
yield of 3aa' to 64% (entry 7). In comparison, the combination
of PdCl2 as the catalyst precursor and 10 mL of water gave 90%
yield of the amine after 24 h (entry 8). In contrast, in the pres-
ence of 1 equivalent of basic diethylamine, the reactivity was
completely inhibited and only the starting material was recov-
ered (entry 9). In conclusion, acid (HCl) or in situ generated HCl
significantly improved the amination reaction of the allylic al-
cohol, whereas addition of basic amines inhibited the reaction.
To compare the reactivity of cinnamyl alcohol and the corre-
sponding amine, the carbonylation of 3aa' using Pd2(dba)3
without any additive was investigated. Indeed, the reaction
proceeded and 11% yield of 3aa could be observed (Table 3,
entry 1). Interestingly, only a slightly increased yield (25%,
entry 2) was obtained by adding 5 mol% of HCl into the reac-
tion media. Surprisingly, by further adding 10 mL of water, the
byproduct of the amination reaction of the allylic alcohol, the
yield of 3aa increased considerably to 93% (entry 3). In this
case, in the presence of halide, water is not only promoting
the amination step, but also promoting the carbonylation step.
Furthermore, the progress of the reaction was monitored by
analysis of samples taken from the reaction mixture. After an
induction period of around 100 min, which could probably be
explained by the in situ generation of Pd0 and HCl by the
water–gas shift reaction, 1a and 2a were quickly consumed
and transformed into the amination product 3aa' in around
200 min (see Figure 1). At the same time, less than 10% of the
final product 3aa was formed. Afterwards, the formation of
Figure 1. Reaction profile of the palladium-catalyzed aminocarbonylation of
allylic alcohol.
Based on the previous mechanistic understandings of palla-
dium-catalyzed Tsuji–Trost-type reactions, we suggest this reac-
tion follows the mechanistic pathway as depicted in Scheme 3.
Basically, this reaction involves two catalytic cycles, the amina-
tion of the allylic alcohol (Cycle A) and the carbonylation of the
allylic amine (Cycle B), both of which are closely related to
each other. At the beginning, the catalytically active allyl palla-
dium species C1 is generated by the reaction of PdCl2 with the
allylic alcohol 1a.[23] At this stage, both CO coordination/inser-
tion and the nucleophilic attack of amine to allyl palladium
species are possible, steps which seem to be controlled by the
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concentration of free amine. At the beginning stage of the re-
action, the concentration of free amine is high, and thus the
aminolysis of the allyl-palladium species is faster, which gener-
ates allylic amine and regenerates the Pd0 species C2. The acti-
vation of allylic alcohol and allyl amine are promoted by the in
situ generated or added acid and regenerate C1 (Cycle A). Like-
wise, the other cycle starts from the oxidative addition of allyl
amine to Pd0 C2, which is assisted by acid and water. With
progress of the reaction, CO insertion to C1 will generate acyl-
palladium species C5. Finally, the aminolysis of the acyl-palladi-
um species affords the desired carbonylation product and re-
generates C2 (Cycle B).
further increase in the reaction temperature to 1208C yielded
the product in 83%. Moreover, cyclic allyl alcohols, such as cy-
clohex-2-enol (1i), reacted smoothly under condition B (51%
isolated yield of 3ia, entry 8).
To highlight the application potential of our developed
method, several industrially relevant, advanced building blocks
were carbonylated. For example, starting from 1j, which con-
stitutes an intermediate from the bulk telomerization of 1,3-
butadiene to 1-octene, 3ja was obtained in 62% isolated yield
(E/Z=80/20, Table 4, entry 9).[24] Moreover, renewables such as
geraniol (1k), nerol (1l), and linalool (1m), which are used in
the perfume and fragrance industry, gave quantitative yield of
the desired amides (E/Z=67/33, 62/38, and 62/38, respectively,
entries 10–12). Noticeably, in all these cases the internal C=C
bond remained intact under such reaction conditions. Further-
more, acyclic diterpene alcohols, for example phytol and iso-
phytol, were successfully transformed into the corresponding
amides in very good yields (95 and 90% yield, respectively,
E/Z=68/32, entries 13 and 14). Farnesol (1p), an example of an
acyclic sesquiterpene, afforded 88% yield of the corresponding
amide (a mixture of four isomers, ratio 15:20:24:41, entry 15).
To note, homofarnesylic acid amide (3pa) can be used for the
synthesis of (Æ)-ambroxan, which is used as amber-like per-
fume material, through an acid-catalyzed cyclization reac-
tion.[7a]
To investigate the influence of electronic effects and the
functional group tolerance of this method, different N-substi-
tuted anilines were reacted with 1a (Scheme 4). With 4-me-
thoxy-N-methylaniline as the substrate, 3ab was obtained in
89% yield. Using anilines with simple electron-withdrawing
groups (F and Cl substituents), the corresponding products
3ac and 3ad were obtained also in good yield (90 and 81%,
respectively). Reaction of the cyclic indoline led to the corre-
sponding 3ae in 65% isolated yield. More sterically demanding
amines such as N-cyclohexylaniline, N-benzyl-4-methoxyaniline,
and N-methyl-2-(trifluoromethyl)aniline were all well tolerated
under these conditions (92, 83, and 90% yield, respectively). Fi-
nally, 10,11-dihydro-5H-dibenzo[b,f]azepine was tested and af-
forded 3ai in 69% yield.
In general, N-alkylation reactions of primary amines are
more challenging because mono- and dialkylation reactions
could take place at the same time. Nevertheless, in the reac-
tion of aniline and our model substrate cinnamyl alcohol,
monoalkylation prevailed, leading to 4aa. However, 1,3-diphe-
nylpyrrolidin-2-one was observed as a side product, which de-
rives from the competitive intramolecular carbonylation reac-
tion at the benzylic position of N-cinnamylaniline. By carefully
selecting an appropriate ligand (4 mol% cataCXiumꢀ PCy L8)
4aa was obtained in 63% isolated yield (Scheme 5). Less-acti-
vated aliphatic allylic alcohols without benzylic stabilization do
not undergo this cyclization reaction. Hence, starting from iso-
butenol (1d) and aniline, 4da was isolated in 72% yield after
48 h heating. With crotyl alcohol (E/Z mixture, 1e) as the sub-
strate, 4ea was selectively obtained (85% yield). Furthermore,
good yields were also obtained when using prenol (1h), gera-
niol (1k), or 2-cyclohexen-1-ol (1i) as the substrate (91, 72, and
89% isolated yield for 4ha, 4ka, and 4ia, respectively). Again,
Scheme 3. Palladium-catalyzed aminocarbonylation of allylic alcohols: pro-
posed reaction pathway.
In order to explore the scope of this novel reaction, a variety
of allylic alcohols were tested (Table 4). 1-Phenylprop-2-en-1-ol
(1b) as a substrate yielded the linear product 3ba in high
yield (95%, entry 1). This clearly indicates that the reaction
goes via an allyl-palladium complex as the reaction intermedi-
ate. Starting from the parent allyl alcohol 1c (3 equiv) the car-
bonylation process led to 92% yield of 3ca (entry 2). However,
using sterically more hindered b-methallyl alcohol (1d) under
standard conditions (condition A), no desired product was ob-
served. Gratifyingly, employing less hindered L10 as ligand
under slightly modified conditions (with 5 mol% TFA as addi-
tive, see condition B), the corresponding product 3da could be
obtained in 40% yield (entry 3). On the other hand, a good
yield was obtained with crotyl alcohol (1e) (84% yield, E/Z=
76/24, entry 4). As expected, but-3-en-2-ol (1 f) as the substrate
gave the identical product (i.e., 3ea=3 fa) in 87% isolated
yield (entry 5). Another example of a 1-substituted allyl alcohol
1g also gave the linear product 3ga, as the final product, in
84% isolated yield (entry 6). Similar to 1d, the di-substituted
alcohol 1h did not afford the desired product using Xantphos
even with TFA as additive. However, using PPh3 L10 as the
ligand, 53% isolated yield was obtained at 1008C (entry 7). A
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Table 4. Palladium-catalyzed aminocarbonylation of allylic alcohols: substrate scope.[a]
Entry
1
Allylic alcohol
Ligand
Additive
Product
Yield [%][e]
1b
1c
1d
1e
1 f
Xantphos
H2O (10 mL)
3ba
95[b]
2
3
4
5
6
7
Xantphos
PPh3
H2O (10 mL)
TFA (5 mol%)
H2O (10 mL)
H2O (10 mL)
H2O (10 mL)
TFA (5 mol%)
3ca
3da
3ea
3 fa
3ga
3ha
92[b,d]
40[b]
Xantphos
Xantphos
Xantphos
PPh3
84 (E/Z=76/24)[b]
87 (E/Z=76/24)[b]
84 (E/Z=82/18)[b]
1g
1h
53[b]
83[c]
8
1i
PPh3
TFA (5 mol%)
3ia
51[c]
9
1ij
Xantphos
PPh3
TFA (5 mol%)
TFA (5 mol%)
3ja
62 (E/Z=80/20)[b]
95 (E/Z=67/33)[c]
10
1ik
3ka
11
12
1l
PPh3
PPh3
TFA (5 mol%)
TFA (5 mol%)
3la
95 (E/Z=62/38)[c]
95 (E/Z=62/38)[c]
1m
3ma
13
1n
PPh3
TFA (5 mol%)
3na
95 (E/Z=68/32)[c]
14
15
1o
1p
PPh3
PPh3
TFA (5 mol%)
TFA (5 mol%)
3oa
3pa
90 (E/Z=68/32)[c]
88[c]
[a] Condition A: 1 (1.5 mmol), 2 (1 mmol), PdCl2 (0.5 mol%, 0.005 mmol), L6 (0.75 mol% 0.0075 mmol), or Condition B: 1 (1.5 mmol), 2 (1 mmol), PdCl2
(0.5 mol%, 0.005 mmol), L10 (2 mol%, 0.02 mol%) in toluene (2 mL), CO (40 bar) for 24 h. [b] 1008C. [c] 1208C. [d] 1 (3 mmol). [e] Yield of the isolated
products, E/Z ratio determined by gas chromatography.
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Conclusion
In conclusion, for the first time, a palladium-catalyzed direct
aminocarbonylation reaction of allylic alcohols has been ach-
ieved. Notably, the reactivity of the catalyst system is signifi-
cantly improved by adding water (or acid) as an additive. Start-
ing from easily available allylic alcohols and aromatic amines,
a variety of b,g-unsaturated amides could be synthesized in
high yields under mild reaction conditions with good function-
al group tolerance (34 examples, 40–95% yield). Mechanistic
studies by performing control experiments reveal the impor-
tant role of halides in this reaction. We expect that this newly
developed catalytic method will inspire synthetic chemists to
apply more carbonylation reactions in fine chemical and phar-
maceuticals syntheses.
Acknowledgements
The Federal Ministry of Education and Research (BMBF) and
Evonik Industries are gratefully acknowledged for their general
support. We would like to thank the analytical department of
LIKAT for support. The supportive discussions with Dr. Qiang
Liu, Dr. Raffaella Ferraccioli, and Jie Liu are gratefully acknowl-
edged.
Scheme 4. Palladium-catalyzed aminocarbonylation of allylic alcohols: scope
of secondary amines. Reaction conditions: 1 (1.5 mmol), 2 (1 mmol), PdCl2
(0.5 mol%, 0.005 mmol), L6 (0.75 mol%, 0.0075 mmol), H2O (10 mL) in tolu-
ene (2 mL), CO (40 bar), 1008C for 24 h, yields of isolated product shown.
this method is shown to be general to different aniline deriva-
tives. Starting from 3-methylbut-2-en-1-ol (1h), anilines bearing
ortho-Br and para-Cl substituents were transformed to the cor-
responding b,g-unsaturated amides with good yields (74 and
80% isolated yields, respectively). More sterically hindered 2-
(1H-pyrrol-1-yl)- and 2-phenyl-anilines were also well tolerated
and afforded selectively the corresponding b,g-unsaturated
amides 4hd and 4he in 85 and 71% yield, respectively.
Keywords: allylic · amide · carbonylation · homogeneous
catalysis · palladium
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Received: March 16, 2016
Published online on && &&, 0000
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FULL PAPER
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Palladium Catalysis
H. Li, H. Neumann, M. Beller*
&& – &&
Palladium-Catalyzed
Aminocarbonylation of Allylic Alcohols
Amino-zing carbonylation! A palladi-
um-catalyzed direct aminocarbonylation
reaction of allylic alcohols is achieved.
Starting from easily available allylic alco-
hols and aromatic amines, a variety of
b,g-unsaturated amides could be syn-
thesized in high yields under mild reac-
tion conditions (34 examples, 40–95%
yield).
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Chem. Eur. J. 2016, 22, 1 – 8
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ꢁ 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
ÝÝ These are not the final page numbers!