Palladium-catalyzed direct arylation of allylamines with simple arenes

Article abstract of DOI:10.1002/cctc.201403019

The Pd(OAc)₂-catalyzed direct C-H bond olefination of unreactive arenes with allylamines in the presence of AgOAc was developed. A variety of allylamines including β-substituted substrates underwent smooth coupling reactions with various arenes

Full text of DOI:10.1002/cctc.201403019

DOI: 10.1002/cctc.201403019
Communications
Palladium-Catalyzed Direct Arylation of Allylamines with
Simple Arenes
[
a, b]
[b]
[b]
[b]
[b]
[b]
Yichao Lei,
Ruiying Qiu, Lingjuan Zhang, Conghui Xu, Yixiao Pan, Xubo Qin,
[b]
[b]
[a]
Huanrong Li, Lijin Xu,* and Yuheng Deng*
The Pd(OAc) -catalyzed direct CÀH bond olefination of unreac-
olefination of simple arenes not containing directing groups,
2
[7]
[8]
[9]
tive arenes with allylamines in the presence of AgOAc was de-
veloped. A variety of allylamines including b-substituted sub-
strates underwent smooth coupling reactions with various
arenes to give exclusively the terminal arylation products in
high yields with excellent regioselectivities and stereoselectivi-
ties. The reaction is compatible with a range of functional
groups in both coupling partners. The carbonyl group in the
allylamine substrates is critical to catalysis, and the high regio-
and stereocontrol observed is attributed to coordination be-
tween the carbonyl O and Pd atoms.
and catalysts based on Pd, Rh, and Ru complexes are no-
table for their high catalytic efficiency, functional group toler-
ance, and value of applications. Among these reported studies,
electron-deficient olefins (e.g.,a, b-unsaturated esters and
amides) and electron-neutral aliphatic olefins and styrenes
have been broadly employed to yield promising results.
Recent reports have demonstrated that other olefins, such as
[
10a–e,h]
[10f]
allyl esters,
enamides,
and trisubstituted cinnama-
[
10g]
tes,
can also undergo direct coupling reactions with simple
arenes to give the target products with different reactivities
and selectivities. In the course of exploring the regioselective
[11]
arylation of olefins, we recently disclosed that the combina-
tion of Pd(OAc)2 and suitable oxidants could catalyze the
highly regioselective direct heteroarylation of allylamines with
thiophenes and furans to give the target products in high
yields (Scheme 1a), and it is noteworthy that the electronic
The efficient construction of allylamines has been the subject
of extensive research over many years, because these amines
are important structural units in many natural products and
pharmaceuticals, and they also serve as important precursors
[
1–3]
for the synthesis of functionalized compounds.
Recent stud-
ies have revealed that biologically and synthetically important
arylated allylamines can be readily accessed through Pd-cata-
lyzed arylation of readily accessible allylamines with aryl
triflates, aryl halides, arenediazonium salts, and arylboronic
acids; furthermore, useful strategies have been developed to
[
4]
control the regioselectivity. However, a preactivation step of
the (hetero)arenes is required in these reactions, and it is clear
that, from the viewpoint of atom economy and efficiency, the
direct cross-coupling between simple (hetero)arenes and allyl-
amines would be a straightforward and more efficient method.
Transition-metal-catalyzed direct CÀH functionalization reac-
tions are currently emerging as powerful rivals to traditional
organic transformations based on prefunctionalized substrates,
Scheme 1. Catalytic direct olefination of arenes with allylamines. FG=Func-
tional group.
[5]
owing to their improved atom economy and efficiency.
Therefore, it is not surprising that transition-metal-catalyzed
direct dehydrogenative coupling reactions of arenes with ole-
fins (also referred to as the Fujiwara–Moritani reaction) has at-
and steric properties of the allylamines have a significant
[11c]
impact on the catalytic activity and regiocontrol.
Encour-
[6]
tracted increasing research interest over the last decades.
Particularly, substantial progress has been made in the direct
aged by this discovery, we became interested in the develop-
ment of a direct coupling reaction of allylamines with simple
arenes. Herein, we report that simple arenes can indeed react
with allylamines in the presence of a Pd(OAc) catalyst in com-
2
[
a] Y. Lei, Prof. Y. Deng
Department of Chemistry, Capital Normal University
Beijing, 100048 (P.R. China)
bination with AgOAc as the oxidant (Scheme 1b) to afford ary-
lated allylamine products in a highly regioselective and stereo-
[12]
E-mail: dyh@mail.cnu.edu.cn
selective manner.
[
b] Y. Lei, R. Qiu, L. Zhang, C. Xu, Y. Pan, X. Qin, Prof. H. Li, Prof. L. Xu
Department of Chemistry, Renmin University of China
Beijing, 100872 (P.R. China)
We began our studies by investigating the arylation of N,N-
Boc)2 allylamine (2a, Boc=tert-butyloxycarbonyl) with
(
Pd(OAc) as the catalyst and Ag CO as the oxidant; benzene
E-mail: xulj@chem.ruc.edu.cn
2
2
3
(
1a) acted as both the coupling partner and the reaction
Supporting Information for this article is available on the WWW under
http://dx.doi.org/10.1002/cctc.201403019.
medium. No reaction was observed in pure benzene (Table 1,
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(
Table 1, entries 19–22), but none of them was superior to
Table 1. Screening conditions for the Pd-catalyzed direct olefination of
[
a]
Pd(OAc) . Recent studies have demonstrated the promoting
2
benzene
(1a)
with
N,N-(Boc)
2
-allylamine
(2a).
effect of carboxylic acids in Pd-catalyzed direct olefination re-
[6]
actions. However, upon adding acetic acid to the current re-
action, the yield of 3aa dropped significantly (Table 1,
entry 23). Further investigation indicated that lowering the re-
action temperature decreased the reactivity as evidenced by
the fact that a reduced yield of 82% was observed at 1208C
[
b]
Entry
Oxidant
Solvent
benzene
benzene/DMF=20:1
benzene/DMSO=20:1
benzene/NMP=20:1
Yield [%]
1
2
3
4
5
6
7
8
Ag
Ag
Ag
Ag
Ag
Ag
Ag
Ag
Ag
Ag
2
2
2
2
2
2
2
2
2
2
CO
3
CO
3
CO
3
CO
3
CO
3
CO
3
CO
3
CO
3
CO
3
CO
3
nd
54
71
nd
nd
nd
31
23
nd
nd
nd
nd
nd
34
91
nd
nd
nd
33
45
50
44
14
82
(
Table 1, entry 24). It should be stressed that in all cases no in-
[4j]
ternal arylation, allylic migration, or partial deprotection was
detected, and only E-configured 3aa was produced.
3
benzene/CH CN=20:1
benzene/THF=20:1
benzene/DMSO=10:1
benzene/DMSO=50:1
DMSO
With the optimal reaction conditions in hand, we next inves-
tigated the direct olefination of 1a with a range of other allyl-
amines (Table 2). It was found that both N,N-diprotected (i.e.,
[
c]
9
1
[
c]
0
DCE/DMSO=20:1
11
BQ
benzene/DMSO=20:1
benzene/DMSO=20:1
benzene/DMSO=20:1
benzene/DMSO=20:1
benzene/DMSO=20:1
benzene/DMSO=20:1
benzene/DMSO=20:1
benzene/DMSO=20:1
benzene/DMSO=20:1
benzene/DMSO=20:1
benzene/DMSO=20:1
benzene/DMSO=20:1
benzene/DMSO=20:1
benzene/DMSO=20:1
12
13
14
15
16
17
18
19
20
21
22
23
24
Ag
Ag
2
O
SO4
[a]
Table 2. Pd-catalyzed direct olefination of 1a with allylamines.
2
AgNO
3
AgOAc
Oxone
K S O
2 2 8
O
2
[
[
[
[
[
[
d]
e]
f]
AgOAc
AgOAc
AgOAc
AgOAc
AgOAc
AgOAc
g]
h]
i]
[
a] Reaction conditions: 1a (2.0 mL), 2a (0.4 mmol), Pd(OAc)
oxidant (1.5 equiv.), co-solvent, 1308C, 24 h. [b] Yield of isolated product.
nd: not detected.[c] 1a: 20 equiv. [d] Pd(OAc) was replaced by Pd(tfa)
e] Pd(OAc) was replaced by PdCl [f] Pd(OAc) was replaced by
Pd(PPh . [g] Pd(OAc) was replaced by Pd (dba) . [h] AcOH: 10 equiv.
i] Reaction temperature: 1208C.
2
(5 mol%),
2
2
.
[
2
2
.
2
3
)
4
2
2
3
[
[
2
a] Reaction conditions: 1a (2.0 mL), 2 (0.4 mmol), Pd(OAc) (5 mol%),
AgOAc (0.6 mmol), DMSO (0.1 mL), 1308C, 4 h. Yields of isolated products
are given. Phth=phthaloyl, Bn=benzyl, Cbz=benzyloxycarbonyl.
entry 1), but the addition of 5% DMF as a co-solvent led to the
exclusive formation of target g-arylated product 3aa in 54%
yield (Table 1, entry 2). Replacing DMF with DMSO gave rise to
a higher yield of 71% (Table 1, entry 3), but the use of other
solvents such as N-methyl-2-pyrrolidone (NMP), CH CN, and
compounds 2b, 2g–i) and N-monoprotected (i.e., compounds
2e, 2 f) allylamines underwent smooth arylation with 1a under
the optimized conditions to give the desired linear products
(Table 2, see compounds 3ab, 3af–ai) in high yields regardless
of the nature of the substituents on the allylic amine nitrogen
atom, and excellent regioselectivities (terminal/internal>99:1)
and stereoselectivities (E/Z>20:1) were observed in the reac-
tions studied. It is noteworthy that the a-substituted allylic
amines (i.e., compounds 2c and 2d) exhibited similar reactivity
and selectivity and exclusively afforded the corresponding
linear arylated allylamine products (Table 2, see compounds
3ac and 3ad) in good yields. Interestingly, under the current
catalytic conditions, 2-(but-3-en-1-yl)isoindoline-1,3-dione (2j)
also successfully participated in the direct coupling reaction to
furnish terminal arylation product 3aj in 61% yield. However,
no reaction was detected in the arylation of very electron-rich
N,N-diethylallylamine (2k), and strong coordination of the ni-
trogen atom to Pd is believed to cause catalyst poisoning,
3
THF was not effective (Table 1, entries 4–6). Increasing or de-
creasing the amount of DMSO resulted in decreased yields
(
Table 1, entries 7 and 8), and if the reaction was performed
with benzene (20 equiv.) in DMSO, no product was observed
Table 1, entry 9). Clearly, a specific amount of DMSO is capable
(
of promoting this direct coupling reaction. On the basis of pre-
vious reports on Pd-catalyzed oxidative reactions, DMSO may
[13]
function as a ligand in the present transformation.
The
mixed solvent of DMSO/1,2-dichloroethane (DCE), which has
been reported to facilitate the Pd-catalyzed direct heteroaryla-
[
11c]
tion of allylic amines with thiophenes and furans,
proved to
be inefficient in this case, as no reaction took place (Table 1,
entry 10). To improve the reaction efficiency, the performance
of other oxidants was examined (Table 1, entries 11–18), and
AgOAc was found to be the best choice, as it provided 3aa in
91% yield (Table 1, entry 15). For comparison, other palladium
salts including Pd(tfa) (tfa=trifluoroacetate), PdCl , Pd(PPh ) ,
2
2
3 4
[11c,d]
and Pd (dba)3 (dba=dibenzylideneacetone) were screened
which thereby inhibits the arylation reaction.
2
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Table 3. Pd-catalyzed direct olefination of substituted arenes with allyl-
amines.
Table 4. Pd-catalyzed direct arylation of b-substituted allylamines with
arenes.
[
a]
[a]
[
2
a] Reaction conditions: 1 (2.0 mL), 2 (0.4 mmol), Pd(OAc) (5 mol%),
AgOAc (0.6 mmol), DMSO (0.1 mL), 1308C, 4 h. Yields of isolated products
are given.
[
2
a] Reaction conditions: 1 (2.0 mL), 2 (0.4 mmol), Pd(OAc) (5 mol%),
displayed complete site selectivity in that only one regioisomer
was detected. 2-(2-Phenylallyl)isoindoline-1,3-dione (4b) and
tert-butyl (2-phenylallyl)carbamate (4c) proved to be viable
substrates, and olefinated arene products 5ab, 5ac, and 5bc
were isolated in satisfactory yields. b-Substituted allylamine 4d
was also observed to afford target product 5ad in an excellent
93%yield. It is noteworthy that these obtained trisubstituted
olefins were confirmed to be of the Z configuration by NMR
spectroscopy. Moreover, these trisubstituted olefins underwent
further arylation to provide tetrasubstituted olefin products.
AgOAc (0.6 mmol), DMSO (0.1 mL), 1308C, 4 h. Yields of isolated products
are given.
Next, we turned our attention to the direct coupling reac-
tions of various substituted arenes with allylamine derivatives,
and the results are summarized in Table 3. As can be seen,
under the current catalysis various monosubstituted arenes
were smoothly olefinated to provide the coupling products in
high yields (Table 3, see compounds 3ba–ea, 3bb, 3cb, 3 fb,
3
gb, and 3ci), and regioisomeric mixtures were observed
upon employing toluene (1b), anisole (1c), chlorobenzene
1d), tert-butylbenzene (1e), and fluorobenzene (1 f) as the
coupling partners, whereas electron-deficient ethyl benzoate
1g) only furnished meta-olefinated product 3gb as a single
For example, under the catalysis of Pd(OAc) , 5ab and 5ad
proceeded smoothly to afford products 6aab and 6aad in
high yields (Scheme 2).
2
(
(
regioisomer. Notably, electron-rich monosubstituted arenes 1b
and 1c, chlorobenzene (1d), and fluorobenzene (1 f) favored
ortho and para olefination, but no ortho olefination was de-
tected in the case of tert-butylbenzene (1e) owing to steric ef-
fects. Disubstituted arene 1h was also reactive, and it provided
a mixture of isomers in high yields (Table 3, see compounds
3
hb and 3hc). Electron-deficient 1,4-difluorobenzene (1i) and
1
,3,5-trifluorobenzene (1j) readily reacted with 2e and 2c, and
Scheme 2. Direct arylation of trisubstituted olefins.
corresponding products 3ib, 3jb, 3ic, and 3jc were isolated in
excellent to good yields. Notably, frequently encountered par-
tial deprotection in the arylation of N,N-diprotected allylamines
did not occur in our hands.
On the basis of the observed experimental results and previ-
[11b–e,14]
The current catalytic system also worked well for the direct
arylation of b-substituted allylamines. As shown in Table 4,
electronically different arenes reacted well with b-substituted
allylamine 4a to generate the coupling products (Table 4, see
compounds 5aa–ca, 5ga–ia, and 5ka) in high yields. Notably,
except for toluene (1b), substituted arenes 1c, 1g–i, and 1k
ous reports,
a plausible mechanism is proposed in
Scheme 3. The process is probably initiated by the reaction of
Pd(OAc) with ArH through CÀH bond activation to afford in-
2
termediate A, which reacts with the allylamine to generate in-
termediate B. Coordination between the carbonyl O atom and
the Pd atom in B promotes highly regioselective migration of
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(silica gel, ethyl acetate/hexane 10:90 to 15:85) to give the pure
product.
Acknowledgements
Financial support from the National Natural Science Foundation
of China (21072225, 21172258, 21372258, and 91127039) is
greatly acknowledged.
Scheme 3. Possible pathway for the direct olefination of arenes with allyl-
amines.
Keywords: allylamines · arenes · direct arylation · palladium ·
regioselectivity
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1
9
0
II
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[
15]
derivatives and vinyl derivatives.
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2
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acted well with differently substituted arenes to give exclusive-
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a range of functionalities in both coupling partners was well
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Experimental Section
General method
Unless otherwise noted, all experiments were performed in air.
1
13
H NMR and C NMR spectra were recorded with a Bruker Model
1
13
Avance DMX 400 spectrometer ( H: 400 MHz, C: 106 MHz). Chem-
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An oven-dried pressure tube was sequentially charged with arene
1
(2.0 mL), allylamine 2 (0.4 mmol), Pd(OAc) (4.5 mg, 0.02 mmol),
2
AgOAc (100 mg, 0.6 mmol), and DMSO (0.1 mL) (5%).The mixture
was heated in the sealed tube and stirred vigorously at 1308C for
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Communications
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Received: December 15, 2014
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Published online on && &&, 0000
ChemCatChem 0000, 00, 0 – 0
www.chemcatchem.org
5
ꢀ 0000 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
&
These are not the final page numbers! ÞÞ

COMMUNICATIONS
Y. Lei, R. Qiu, L. Zhang, C. Xu, Y. Pan,
X. Qin, H. Li, L. Xu,* Y. Deng*
&& – &&
Palladium-Catalyzed Direct Arylation
of Allylamines with Simple Arenes
II
CHa CHa CHa: The Pd -catalyzed direct
high regioselectivities and stereoselec-
tivities. A range of functional groups
(FGs) in both coupling partners is well
tolerated. The carbonyl group in the
allylamine substrates is critical to
catalysis.
arylation of allylamines with simple
arenes is developed by using Pd(OAc)2
as the catalyst and AgOAc as the oxi-
dant. The reaction proceeds smoothly
and provides the target products with
&
ChemCatChem 0000, 00, 0 – 0
www.chemcatchem.org
6
ꢀ 0000 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
ÝÝ These are not the final page numbers!