Hydroarylation of N-Allenyl Derivatives Catalyzed by Copper**

Article abstract of DOI:10.1002/ejoc.202001333

An additive-free copper catalytic system was used to perform the addition of (hetero)aryl nucleophiles to N-allenyl derivatives. This intermolecular C–C bond formation occurs with both complete regio- and stereoselectivity to afford the linear (E) allylic

Full text of DOI:10.1002/ejoc.202001333

European Journal of Organic Chemistry
Accepted Article
Accepted Article
Title: Hydroarylation of Allenyl Derivatives Catalyzed by Copper
Authors: Racha Abed Ali Abdine, Lucas Pages, Marc Taillefer, and
Florian Monnier
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1/2020

European Journal of Organic Chemistry
10.1002/ejoc.202001333
FULL PAPER
DOI: 10.1002/adsc.202((will be filled in by the editorial staff))
Hydroarylation of N-Allenyl Derivatives Catalyzed by Copper
#,a
#,a
a,
a, b,
Racha Abed Ali Abdine, Lucas Pagès, Marc Taillefer, * and Florian Monnier *
a
Ecole Nationale Supérieure de Chimie de Montpellier, Institut Charles Gerhardt Montpellier UMR 5253, Univ.
Montpellier, CNRS, ENSCM, 8 rue de l’Ecole Normale, Montpellier 34296 Cedex 5, France.
E-mail : marc.taillefer@enscm.fr; florian.monnier@enscm.fr
Institut Universitaire de France, IUF, 1 rue Descartes, Paris 75231 Cedex 5, France.
b
#
These two authors contributed equally to this work.
Received: ((will be filled in by the editorial staff))
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201######.((Please
delete if not appropriate))
Abstract. A additive-free copper catalytic system was
used to perform the addition of (hetero)aryl nucleophiles
to N-allenyl derivatives. This intermolecular C-C bond
formation occurs with both complete regio- and
stereoselectivity to afford the linear (E) allylic product
with moderate to excellent yields. This atom economical
method is the first example of hydroarylation of allenes
catalyzed by copper.
anti-Markovnikov product (Scheme 1, equation 1).
Other groups reported hydroarylation reactions with
various nucleophilic partners such as aryl boronic
[
44]
[45]
acids ArB(OH)2, aryl boronic esters ArB(OR)2 or
[
46]
aryl halides ArX allowing an ipso-arylation. These
methods allowed the addition of a wide scope of aryl
partners selectively on the central carbon of the allene,
affording then either the endo- or the exo-olefinic
product (Scheme 1, equation 2). These two regio-
divergent pathways are providing interesting products
that could be further functionalized through either the
C-C double bond or the (hetero)aryl group.
Keywords: allenes; copper; hydroarylation; allylic
compounds, arenes, homogeneous catalysis
State-of-the-art
M
Allylic or vinylic molecules are highly valuable
H
[
1]
(
1)
R
•
+
R
intermediates which are easy-to-prepare through
transition metal-catalyzed hydrofunctionalization of
Het
Het
[
2–4]
monosubstituted allenes.
strategy usually
This atom economical
occurs without any
M = Pt, Au, Sc, Pd, Rh, Ir, Co, Ru, Ni, Mn, Fe.
M
prefunctionalization and with very high chemo-, regio-
and stereospecificity. Hydrofunctionalization of
allenes mainly allowed the selective formation of C-N,
Z
(2)
R
•
+
R
R
Het
and/or
Het
Het
[
2,3,5–8]
Z = B(OH)
Z = I, Br : M = Pd
2
/ B(OR)
2
:
M = Pd, Pt, Rh, Ni
C-O and C-C bond.
The latter being performed
through the addition of pronucleophiles such as
[
9–12]
[13–16]
[17–19]
[20–
malonates,
nitriles,
alkynes,
alkenes
This work
2
2]
and aryl derivatives. The reaction of aromatic
Cu
H
R
R
compounds with allenes, known as hydroarylation
reaction, consists in adding an aryl moiety to a C-C
double bond, and constitutes a powerful tool to form a
(3)
N
•
+
Het
R
N
Het
R
R’
R’
N-allenyl derivatives
Aryls, Pyrroles, Indoles
Anilines, Thiophenes
Linear (E) compound
3
2
Csp -Csp bond in regio- and stereoselective manner.
The first example of hydroarylation of allenes with
ArH catalyzed by a transition metal was described by
Scheme 1. Metal-catalyzed hydroarylation of allenes:
known methods and pathway described herein with Cu
catalysis
[
23]
the group of Panunzi with a platinum(II) catalyst.
[
24,25]
Since then, a lot of different transition metals (Sc,
[
26]
[27–30]
[31]
[32]
[33]
[34]
[35,36]
Pd, Rh,
Ir, Co, Ru, Ni, Mn
and
[
37]
Fe ) have also been used to perform hydroarylation
of allenes with aryl nucleophiles (Scheme 1),
especially from cationic gold(I) catalysts that are well
Herein, we report an unprecedented copper-catalyzed
hydroarylation of allenes illustrated by the addition of
aryl and heteroaryl derivatives on N-allenyl
compounds. Based on our previous works on copper-
[
38–43]
known as π-acid complexes.
Most of these
hydroarylation methods are limited to electron-rich
aryl nucleophiles and afford the linear product i.e. the
[47–55]
catalyzed hydrofunctionalization of allenamides,
we began to study the model reaction between N-
1
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European Journal of Organic Chemistry
10.1002/ejoc.202001333
allenyl-2-pyrrolidinone
trimethoxybenzene 2a under various experimental
conditions (Table 1).
1a
with
1,3,5-
14, table 1) in hand, we first explored the scope of the
method for the hydroarylation of allenamide 1a with
various readily available (hetero)aryl compounds 2a-i
(Scheme 2). Noteworthy that obtained compounds are
enamide-type molecules which constitute a versatile
building block for medicinal chemistry and for total
[
56]
synthesis of natural products.
Table 1. Hydroarylation of 1a with 2a: Selected data for
reaction parametric study.a
O
OMe
O
OMe
O
[
Cu] x mol%
O
N
•
N
H
Cu(CH3CN)4PF6 (10 mol%)
CH3CN (0.5M)
+
•
+
N
N
Het
R
Het
R
MeO
OMe
MeO
3aa
OMe
solvent, T °C
8h
1
00°C, 18h
1
1
a
2a
1
a
2a-i
3aa-3ai
solvent
T
[Cu]
x
yield
[b]
(
0.5M)
(°C)
(%)
O
OMe
O
OMe
O
OMe
1
2
3
4
5
6
7
8
9
1,4-dioxane
THF
25
25
CuI
CuI
20
20
20
20
0
0
N
N
N
10
17
23
0
MeO
OMe
OMe
OMe
OMe
DMF
25
CuI
3aa (99%)b
3ac (67%)b
ꢀ
3ab (90%)
CH
CH
CH
CH
CH
CH
CH
CH
CH
CH
CH
CH
3
CN
3
CN
3
CN
3
CN
3
CN
3
CN
3
CN
3
CN
3
CN
3
CN
3
CN
3
CN
25
CuI
O
O
25
-
O
S
S
N
N
25
CuOAc
Cu(OTf)
20
20
10
20
20
20
10
5
13
16
41
51
76
90
88
49
N
N
25
2
MeO
MeO
OMe
3ae (88%)
3af (41%)b
25
Cu(OTf)
2
.PhH
3ad (71%)
25
Cu(CH
Cu(CH
Cu(CH
Cu(CH
Cu(CH
Cu(CH
Cu(CH
3
CN)
3
CN)
3
CN)
3
CN)
3
CN)
3
CN)
3
CN)
4
PF
4
PF
4
PF
4
PF
4
PF
4
PF
4
PF
6
6
6
6
6
6
6
O
O
N
O
N
1
0
80
ꢀ
ꢀ
ꢀ
N
N
N
N
1
1
1
1
1
1
2
3
4
5
100
100
100
100
100
Br
OMe
3
ag (73%)
3ah (30%)b
3ai (45%)b
[
c]
10
10
57
aꢀReactionꢀconditions:ꢀ1aꢀ(0.5ꢀmmol),ꢀ2a-iꢀ(1.2ꢀequiv,ꢀ0.6ꢀmmol,ꢀ
unlessꢀ otherwiseꢀ notified),ꢀ Cu(CH CN) PF ꢀ (10ꢀ mol%,ꢀ
.05ꢀmmol),ꢀCH CNꢀ(0.5M,ꢀ1mL),ꢀargon,ꢀ100°C,ꢀ18h.ꢀIsolatedꢀ
yields.ꢀ bꢀ Reactionꢀ performedꢀ withꢀ 2ꢀ equiv,ꢀ 1ꢀ mmolꢀ ofꢀ arylꢀ
partnerꢀ2.ꢀ
[d]
>99
3
4
6
a
Reaction conditions: 1a (0.5 mmol), 2a (1.2 equiv, 0.6 mmol)
and catalyst (0.025 to 0.1 mmol) were placed in a screw tube under
argon in 1 mL of solvent for 18h at 25 to 100°C. NMR yields
using 4-iodoanisole as internal standard. The mixture was reacted
0
3
b
c
d
for 10 hours. Reaction performed with 1 mmol, 2 equiv of 2a.
Scheme 2. Cu(CH
various (hetero)aryl compounds 2a-i with allene 1a.
3
CN)
4
PF -catalyzed hydroarylation of
6
a
We initially tested the reaction at 25 °C with 20 mol%
of CuI as a catalyst in various solvents: 1,4-dioxane,
THF, DMF and acetonitrile (entries 1-4, table 1). The
latter was then considered as our reference solvent as
it gave the desired product 3aa in 23% yield. A control
experiment was conducted to prove that no reaction is
occurring without any copper salts (entry 5, table 1).
Different copper sources were then investigated, and
The reaction of both 1,3,5-trimethoxybenzene 2a and
1
,2,4-trimethoxybenzene 2b with 1a gave the
formation of 3aa and 3ab, respectively in quantitative
>99%) and in 90% isolated yields. Whereas 1,3-
(
dimethoxybenzene 2c afforded 3ac with a lower yield
of 67%, 1,4-dimethoxybenzene and anisole did not
yield the desired product. Different types of N-
(pyrrole, indole) or S-containing (thiophenes)
heteroaromatic compounds were also successfully
engaged in the reaction with 1a, affording products
Cu(CH
aa (entries 6-9, table 1). We observed that the higher
the temperature, the better the yield up to 100°C
entries 9-11, table 1). We then reduced the catalyst
loading, and observed at this temperature no major
difference between 10 or 20 mol% of Cu(CH CN) PF
3
CN)
4
PF allowed the best rate of formation of
6
3
(
3ad to 3ag in medium to excellent yields. Other
3
4
6
heteroaromatic substrates did not provided any
product under these conditions, such as substituted
pyridines, toluene and 1,3,5-trimethylbenzene. The
meta-substituted N,N-dimethylanilines 2h and 2i
afforded the corresponding products 3ah and 3ai in
moderate yields. It is interesting to notice that 3ah
could be potentially involved in further cross-coupling
reaction through its aryl bromide moiety. Noteworthy
while the yield significantly decreased with only 5
mol% of copper (entries 12-13, table 1). Tests
performed at 100 °C with 10 mol% of Cu(CH
showed that the reaction is not complete after 10 hours
entry 14, table 1). Finally, adding 2 equiv instead of
.2 equiv of aryl reagent 2a allowed us to further
3
CN)
4
PF
6
(
1
increase the yield of 3aa (entry 15, table 1). The
reaction was found to be totally stereo- (only the (E)
product was obtained) and regioselective as the
addition occurred only on the terminal carbon of the
allene. With these optimized conditions (entry 12 and
1
that analysis of H NMR spectra clearly showed the
exclusive formation of one product with the (E)
2
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European Journal of Organic Chemistry
10.1002/ejoc.202001333
configuration of the double bond (see supporting
information).
R
H
Cu(CH
3
CN)
4
PF
6
(10 mol%)
R
N
•
N
+
Het
Het
O
EDG
R
R
O
Z
1
00°C
R’
R’
CH
3
CN (0.5M), 18h
Z
N
N
•
1
2
3
Het
R
R
R
[Cu]
O
OMe
O
O
+
H+
S
N
N
N
N
O
O
O
EDG
MeO
OMe
MeO
[Cu]
[Cu]
OMe
O
Z
O
•
3
ba (60%)
3be (58%)
3bf (62%)
Het
R
Z
N
O
N
O
N
R
R
N
O
N
N
O
Br
EDG
EDG
-H+
[Cu]
H
H
3
bg (61%)
3
bh (80%)
O
Z
Het
R
Het
R
N
O
N
OMe
O
O
N
R
S
S
S
ꢀ
N
N
O
O
N
O
MeO
OMe
Br
ꢀ
Scheme 4. Plausible mechanism for the copper-catalyzed
3
ca (67%)
3cg (64%)
3ch (68%)
hydroarylation of N-allenyl derivatives.
ꢀ
aꢀ
Reactionꢀ conditions:ꢀ 1ꢀ (0.5ꢀ mmol),ꢀ 2ꢀ (2ꢀ equiv,ꢀ 1ꢀ mmol),ꢀ
Cu(CH
3
CN)
4
PF
6
ꢀ (10ꢀ mol%,ꢀ 0.05ꢀmmol),ꢀ CH
3
CNꢀ (0.5M,ꢀ 1mL),ꢀ In summary, we reported anꢀunprecedentedꢀcopper-
catalyzedꢀ hydroarylationꢀ ofꢀ allenesꢀ illustratedꢀ byꢀ
argon,ꢀ100°C,ꢀ18h.ꢀIsolatedꢀyields.ꢀ
theꢀ additionꢀ ofꢀ (hetero)arylꢀ nucleophilesꢀ onꢀ N-
Scheme 3. Extension to other N-allenyl derivatives and
cross reactivity.
a
allenylꢀ derivativesꢀ which afford selectively (E)-
allylic compounds with medium to excellent yields in
a total atom economical fashion. Various readily
available aromatic compounds were successfully
engaged in the reaction with allene substrates, showing
the good tolerance of the methodology. Nevertheless,
we noticed that electron-rich substrates are required
for the reaction to proceed, which is consistent with the
Other N-allenyl derivatives bearing either a carbamate
1b or a sulfonamide moiety 1c were then successfully
engaged in this copper-catalyzed hydroarylation,
affording the corresponding products in good to high
yields (Scheme 3). These substrates 1b and 1c afforded
the corresponding linear (E) products with electron-
rich arene (3ba, 3ca), thiophene derivatives (3be), N-
phenyl pyrrole (3bf), indole derivatives (3bg, 3cg) and
aniline derivatives (3bh, 3ch) in moderate to good
literature and
E
S Ar-type mechanism. Further
investigations on the potential of copper-catalyzed
systems for hydrofunctionalization of allenes will be
reported in due course. ꢀ
yields with
a
total control of regio- and
stereoselectivity.
Experimental Section
Basedꢀ onꢀ ourꢀ previousꢀ studies[49,51]ꢀ andꢀ
mechanismsꢀdescribedꢀinꢀtheꢀliterature,[38,43,57]ꢀweꢀ
suggestꢀ asꢀ theꢀ firstꢀ stepꢀ ofꢀ theꢀ processꢀ theꢀ
coordinationꢀ ofꢀ theꢀ copperꢀ toꢀ theꢀN-allenylꢀ
derivativeꢀ throughꢀ theꢀ assistingꢀ groupꢀ andꢀ theꢀ
centralꢀ carbonꢀ ofꢀ theꢀ allene.ꢀ Weꢀ assumeꢀ thatꢀ theꢀ
electronꢀrichꢀarylꢀisꢀthenꢀreactingꢀasꢀaꢀnucleophileꢀ
onꢀ theꢀ terminalꢀ positionꢀ ofꢀ theꢀ allene.ꢀ Thisꢀ
electrophilicꢀaromaticꢀsubstitutionꢀ(S
theꢀformationꢀofꢀaꢀplausibleꢀWhelandꢀintermediate,ꢀ Tetrakis(acetonitrile)copper(I)
whichꢀ undergoesꢀ intoꢀ protodecuprationꢀ toꢀ affordꢀ
selectivelyꢀ theꢀ(E)-product.ꢀ Theꢀ needꢀ ofꢀ electronꢀ
donatingꢀ groupsꢀ inꢀ adequateꢀ positionsꢀ onꢀ theꢀ
Detailed experimental procedures and characterization data
for all new compounds are provided (PDF).
General procedure for hydroarylation of N-allenyl
derivatives: An oven-dried Schlenk flask of appropriate
size equipped with a magnetic stirring bar is placed under
vacuum then back-filled with argon. This procedure is
E
Ar)ꢀleadsꢀtoꢀ
repeated three times. Under
a
stream of argon,
hexafluorophosphate
Cu(CH
3
CN)
4
PF
6
(10 mol%) is added, followed by the
(hetero)aryl nucleophile (1.2 equiv or 2 equiv as mentionned
in main text), acetonitrile (0.5M, 1 mL) and the allene (0.5
mmol, 1 equiv). The Schlenk flask is then sealed under a
positive pressure of argon, stirred and heated at 100°C for
18h. After allowing the reaction to cool down to room
temperature, either 1,3,5-trimethoxybenzene (0.33 equiv,
(hetero)arylꢀ substrateꢀ isꢀ consistentꢀ withꢀ thisꢀ
mechanismꢀproposalꢀ(Schemeꢀ4).ꢀ
0.165 mmol, 27.8 mg) or 4-iodoanisole (0.33 equiv, 0.165
3
This article is protected by copyright. All rights reserved.

European Journal of Organic Chemistry
10.1002/ejoc.202001333
mmol, 38.6 mg) is added as internal standard. The reaction
mixture is then diluted in ca. 3 mL of dichloromethane and
extracted with water. The organic layer is dried over
[18]
C. P. Grugel, B. Breit, Org. Lett. 2018, 20, 1066–
1069.
[19]
L. Jeanne-Julien, G. Masson, R. Kouoi, A.
Regazzetti, G. Genta-Jouve, V. Gandon, E.
Roulland, Org. Lett. 2019, 21, 3136–3141.
anhydrous magnesium sulfate MgSO
4
and the solvent is
removed under vacuum. The residue is then purified by
triethylamine NEt
chromatography.
3
treated silica gel column
[20]
[21]
[22]
W. Li, N. Chen, J. Montgomery, Angew. Chem.
Int. Ed. 2010, 49, 8712–8716.
Acknowledgements
S. Parisotto, L. Palagi, C. Prandi, A. Deagostino,
Chem. Eur. J. 2018, 24, 5484–5488.
Financial support provided by École Nationale Supérieure de
Chimie de Montpellier (ENSCM, PhD fellowship for RA and LP),
Institut Universitaire de France (IUF, FM) and Centre National
de la Recherche Scientifique (CNRS) are warmly acknowledged
with thanks.
G. Xu, B. Fu, H. Zhao, Y. Li, G. Zhang, Y. Wang,
T. Xiong, Q. Zhang, Chem. Sci. 2019, 10, 1802–
1806.
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European Journal of Organic Chemistry
10.1002/ejoc.202001333
FULL PAPER
Hydroarylation of N-Allenyl Derivatives
Catalyzed by Copper
The regio- and stereoselective addition of
(
hetero)aryl nucleophiles to N-allenyl derivatives is
described under copper catalysis. represents the
first example of hydroarylation of allenes catalyzed
by copper.
Cu
R
H
R
N
•
+
N
Het
R
Het
R
R’
R’
17 examples
30-99%
Regioselective
Stereoselective
100% atom-economical
KEYTOPIC: Allene hydroarylation
Racha Abed Ali Abdine, Lucas Pagès, Marc
Taillefer,* and Florian Monnier*
6
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