Copper(II) catalyzed allylic amination of terpenic chlorides in water

Article abstract of DOI:10.1016/j.catcom.2011.12.019

A highly efficient method for the synthesis of allylic amines from terpenic chlorides by cheap copper (II) as catalyst in water has been developed. Allylic chlorides react with high regioselectivity in the presence of secondary amines, under mild conditions to give N-allylic amines in excellent yields.

Full text of DOI:10.1016/j.catcom.2011.12.019

Catalysis Communications 19 (2012) 46–50
Contents lists available at SciVerse ScienceDirect
Catalysis Communications
journal homepage: www.elsevier.com/locate/catcom
Short Communication
Copper(II) catalyzed allylic amination of terpenic chlorides in water
Brahim Boualy a, Mohamed Anouar Harrad a, Soufiane El Houssame b, Larbi El Firdoussi a,
,
⁎
Mustapha Ait Ali a, Abdallah Karim a
a
Equipe de Chimie de Coordination et Catalyse, Département de Chimie, Faculté des Sciences Semlalia, BP 2390, 40001 Marrakech, Morocco
b
Université Hassan 1er, Faculté Polydisciplinaire de Khouribga, BP: 145-25000 Khouribga, Morocco
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 26 May 2011
Received in revised form 15 December 2011
Accepted 19 December 2011
Available online 27 December 2011
A highly efficient method for the synthesis of allylic amines from terpenic chlorides by cheap copper (II) as
catalyst in water has been developed. Allylic chlorides react with high regioselectivity in the presence of sec-
ondary amines, under mild conditions to give N-allylic amines in excellent yields.
© 2011 Elsevier B.V. All rights reserved.
Keywords:
Allylic amination
Allylic chlorides
Copper
Water
Monoterpenes
1. Introduction
but the addition of surfactants such as cetyltrimethylammonium bro-
mide was required [15,16]. Moreover, Feuerstein et al. showed that
Allylic amines are important products found in many naturally oc-
curring compounds such as gabaculin [1], oryzoxymicin [2], and cyto-
sinine [3]. The development of easier and selective methods for the
synthesis of allylic amines merits thorough investigation [4], since di-
rect reaction require rather drastic conditions [5]. Transition metal-
promoted allylic amination of alkenes offers an attractive route to
prepare amines via C\N bond formation [6]. However, complexes
of palladium are found to be most effective for selective processes, al-
though complexes of iron, nickel, and copper are also used for allylic
amination [7–9].
The catalytic activity of a number of copper complexes and salts
toward allylic amination of alkenes using phenylhydroxylamine as
the nitrogen fragment donor has been investigated [10]. The copper
(I) complex [Cu(CH3CN)4]PF6 catalyzes the allylic amination of al-
kenes by aryl hydroxylamine in fair to moderate yields [6].
Recently Clark et al. reported that asymmetric allylic amination
can be achieved by reaction of an alkene with a peroxycarbamate cat-
alyzed by a chiral copper bis-oxazoline complex [11].
Tedicyp–palladium complex provides a convenient catalyst for the al-
lylic amination reaction in water [17].
A large number of biologically active natural compounds consist of
a nitrogen-containing heterocycle and occupy a leading position in
medicinal therapy [18,19]. In particular, allylic aminated terpenoids
because of their effects of inhibiting tumor cell growth in vivo and
vitro [20–22] and it serves as a tool for the synthesis of new enantio-
merically pure compounds [23–25].
Baruah et al. have developed a new method for the conversion of
allylic halides to allylic amines by using a mixture of copper (II) per-
chlorate and copper metal [26]. They found significant differences
in the product ratios of the isomeric corresponding allylic amines
formed.
In the course of our studies on monoterpenes and their deriva-
tives, we have recently reported an extremely efficient method for
the preparation of various allylic terpenic chlorides [23]. Following
our catalysis objective on the coupling of various amines and natural
allylic compounds [27], we herein, with a view to extend the poten-
tial use of these terpenic chlorides, focused our efforts on the allylic
amination reaction using copper complexes. Our results show that
monoterpenic chlorides react to give the corresponding allylic amines
with a good to excellent yields. The optical purity of the reaction
products has been also discussed. The use of water as solvent for
this reaction is of interest in sustainable chemistry. It provides in ad-
dition noticeable advantages in terms of economical, environmental
and safety reasons.
An efficient method to perform the allylic substitution in water
has been reported [12–14]. It should be noted that, Sinou et al. and
Kobayashi et al. have reported that palladium-catalyzed alkylation
also occurred in water in the presence of non-water-soluble ligands,
⁎
Corresponding author. Tel.: +212 524 434649; fax: +212 524 437408.
E-mail address: elfirdoussi@ucam.ac.ma (L. El Firdoussi).
1566-7367/$ – see front matter © 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.catcom.2011.12.019

B. Boualy et al. / Catalysis Communications 19 (2012) 46–50
47
2. Experimental section
2.7. 4-(4-Isopropenylcyclohex-1-enylmethyl)morpholine 4b
2.1. General
[α]D20=−21.1 (c=1.5, CHCl3); 1H NMR: δ 5.6 (1H, m), 4.7 (2H, m),
3.6 (4H, m), 2.8 (2H, s), 2.3 (4H, m), 1.6 (3H, s); 13C NMR: δ 149.3 (Cq),
134.5 (CH_), 124.3 (Cq), 108.5 (CH2_), 66.8 (O\CH2\), 65.8
(CH2\N), 53.5 (CH2\N), 41.1 (CH\), 31.4 (\CH2\), 27.3 (\CH2\),
27.3 (\CH2\), 21.1 (\CH3); MS, m/z: 221 (M+, 100).
Optical rotations were measured on a Perkin Elmer 241 polarime-
ter. NMR studies were performed on a Bruker Avance 300 spectrom-
eter in CDCl3. Chemicals shifts are given in ppm relative to external
TMS and coupling constant (J) in Hz. Mass spectra were recorded on
a GC–MS Varian Polaris-Q mass spectrometer. The reaction mixtures
2.8. N-ethyl-N-((4-(prop-1-en-2-yl)cyclohex-1-enyl)methyl)ethanamine 4c
were analyzed on
a Trace GC TheromFinnigan chromatograph
equipped with an FID detector. GC parameters for capillary columns
BP (25 m×0.25 mm, SGE): injector 250 °C; detector 250 °C; oven
70 °C for 5 min then 3 °C min−1 until 250 °C for 30 min; column pres-
[α]D20 =−9.3 (c=1.5, CHCl3). 1H NMR: δ 5.6 (1H, m), 4.9 (2H, m),
3.1 (2H, s), 2.6 (4H, q, J=7.18), 1.7 (3H, s), 1.1 (6H, t, J=7.18); 13C
NMR: δ 149.1 (Cq), 134.7 (CH_), 124.3 (Cq), 109.1 (CH2_), 63.8
(CH2\N), 53.1 (CH2\N), 41.2 (\CH\), 31.3 (\CH2\), 27.3
(\CH2\), 27.2 (\CH2\), 20.2 (\CH3), 15.1 (\CH3); MS, m/z: 207
(M+, 100).
sure 20 kPa, column flow 6.3 mL min−1; linear velocity 53.1 cm s−1
;
and total flow 138 mL min−1. Liquid chromatography was performed
on silica gel (Merk 60, 220–440 mesh; eluent: hexane/ethylacetate).
EI mass spectra were recorded on an AMD 402 spectrometer (70 eV,
AMD Intectra GmbH). Analytical thin-layer chromatography (TLC)
was conducted on Merck aluminum plates with 0.2 mm of silica gel
60F-254. All the reagents and solvents used in the experiments
were purchased from commercial sources as received without further
purification (Aldrich, Acros).
2.9. 2-Methyl-5-(1-pyrrolidin-1-ylmethylvinyl)cyclohex-2-enone 6a
[α]D20 =−57.4 (c=2.1, CHCl3); 1H NMR: δ 6.55 (1H, m), 5.20 (1H,
s), 5.10 (1H, s), 3.12 (2H, m), 2.92 (2H, s), 2.61 (4H, m), 2.38 (3H, s),
1.6 (4H, m); 13C NMR: δ 199.5 (C_O), 146.5 (Cq), 144.2 (CH_), 132.8
(Cq), 112.7 (CH2_), 63.4; 62.1 (CH2\N), 44.2 (CH2\N), 39.7
(\CH\), 31.2 (\CH2\), 23.4 (\CH2\), 16.5 (\CH3); MS, m/z: 219
(M+, 100).
2.2. Catalytic allylic amination of allylic chlorides
In a typical experiment, to a stirred solution of allylic chloride
(0.5 mmol), triethylamine (0.25 mmol) and Cu(II) (0.005 mmol) in
25 mL of water was added secondary amine (1 mmol) at room tem-
perature, and the reaction mixture was stirred for 12 h. After diluting
with H2O (25 mL) and CH2Cl2 (25 mL), the two layers were separated
and the aqueous layer was extracted with CH2Cl2 (2×10 mL). The
combined organic layer was dried over anhydrous Na2SO4 and the
solvent was removed under reduced pressure. Pure allylic amines
were obtained by column chromatography over silica gel using a mix-
ture of hexane/ethylacetate (8/2) as eluent.
2.10. 2-Methyl-5-(1-morpholin-4-ylmethylvinyl)cyclohex-2-enone 6b
[α]D20 =−53.9 (c=2.5, CHCl3); 1H NMR: δ 6.35 (1H, m), 5.22 (1H,
s), 5.13 (1H, s), 3.82 (4H, m), 3.10 (2H, s), 2.84 (2H, m), 2.58 (4H, m),
2.38 (3H, s); 13C NMR: δ 198.6 (C_O), 146.5 (Cq), 143.2 (CH_), 132.9
(Cq), 112.2 (CH2\), 66.8 (CH2\O), 62.1 (CH2\N), 59.2 (CH2\N), 44.2
(\CH\) 40.7 (\CH2\), 32.2 (\CH2\), 17.5 (\CH3); MS, m/z: 235
(M+, 100).
2.11. 5-(3-(diethylamino)prop-1-en-2-yl)-2-methylcyclohex-2-enone 6c
[α]D20 =−55.2 (c=2.5, CHCl3); 1H NMR: δ 6.45 (1H, m), 5.32 (1H, s),
5.22 (1H, s), 3.02 (2H, m), 2.88 (2H, m), 2.61 (4H, q, J=7.23), 2.31 (3H,
s), 1.08 (6H, t, J=7.23); 13C NMR: δ 199.7 (C_O), 146.4 (Cq), 145.0
(\CH_), 132.1 (Cq), 110.9 (CH2_), 63.1 (CH2\N), 53.3 (CH2\N),
44.3 (\CH\), 38.7 (\CH2\), 31.2 (\CH2\), 17.4 (\CH3), 14.8
(\CH3); MS, m/z: 221 (M+, 100).
2.3. 4-(2-Phenylallyl)morpholine 2a
1H NMR: δ 7.6 (2H, m), 7.4 (3H, m), 5.6 (1H, s), 5.5 (1H, s), 3.2 (2H,
s), 2.1 (4H, m), 1.6 (4H, m); 13C NMR: δ 143.6 (Cq), 140.0 (C_), 128.4
(CH ar), 126.6 (CH), 125.0 (CH), 115.3 (CH2_), 63.8 (CH2\O), 60.5
(CH2\N), 53.2 (CH2\N); MS, m/z: 203 (M+, 100).
2.12. 1-(3,7-Dimethylocta-2,6-dienyl)pyrrolidine 8a
2.4. 1-(2-Phenylallyl)pyrrolidine 2b
1H NMR: δ 5.32 (1H, t, J=6.8 Hz), 5.12 (1H, t, J=6.7 Hz), 2.79 (2H,
d, J=6.7 Hz), 2.53 (4H, m), 2 (2H, m), 1.94 (2H, m), 1.75 (4H, m), 1.68
(3H, s), 1.62 (3H, s), 1.50 (3H, s); 13C NMR: δ 139.7 (Cq), 133.9 (Cq),
124.2 (CH_), 121.9 (CH_), 62.3 (CH2\N), 58.0 (CH2\N), 39.7
(\CH2\), 26.4 (\CH2\), 25.7 (\CH2\), 23.7 (\CH3), 17.3 (\CH3),
15.7 (\CH3); MS, m/z: 207 (M+, 100).
1H NMR: δ 7.6 (2H, m); 7.4 (3H, m); 5.6 (1H, s); 5.5 (1H, s); 3.4
(2H, s); 3.6 (4H, m); 2.4 (4H, m); 13C NMR: δ 143.4 (Cq), 139.7 (Cq)
127.8 (CH), 125.6 (CH), 124.0 (CH), 115.3 (CH2_), 66.8 (CH2\N),
60.4 (CH2\N), 24.2 (CH2); MS, m/z: 187 (M+, 100).
2.5. N,N-diethyl-2-phenylprop-2-en-1-amine 2c
2.13. 4-(3,7-Dimethylocta-2,6-dienyl)morpholine 8b
1H NMR: δ 7.4 (2H, m), 7.3 (3H, m), 5.7 (1H, s), 5.6 (1H, s), 3.0 (2H,
s), 2.4 (4H, q, J=7.11), 0.9 (6H, t, J=7.11); 13C NMR: δ 145.2 (Cq),
140.1 (Cq), 127.2 (CH), 125.2 (CH), 124.0 (CH), 114.3 (CH2_), 60.8
(CH2\N), 54.4 (CH2\N), 15.2 (\CH3); MS, m/z: 189 (M+, 100).
1H NMR: δ 5.32 (1H, t, J=6.8 Hz), 5.12 (1H, t, J=6.7 Hz), 3.6 (4H,
m), 2.87 (2H, d, J=6.7 Hz), 2.53 (4H, m), 2 (2H, m), 1.94 (2H, m),
1.68 (3H, s), 1.62 (3H, s), 1.50 (3H, s); 13C NMR: δ 139.7 (Cq), 133.9
(Cq), 124.2 (CH_), 121.9 (CH_), 66.8 (O\CH2), 62.3 (CH2\N), 54.0
(CH2\N), 41.1 (\CH2\), 26.4 (\CH2\), 25.7 (\CH3), 22.7 (\CH3),
17.3 (\CH3); MS, m/z: 223 (M+, 100).
2.6. 1-(4-Isopropenylcyclohex-1-enylmethyl)pyrrolidine 4a
[α]D20=−13.3 (c=2.1, CHCl3); 1H NMR: δ 5.7 (1H, m), 5.1 (2H, m),
3.1 (2H, s), 2.6 (4H, m), 1.8 (3H, s), 1.6 (4H, m); 13C NMR: δ 148.6 (Cq),
137.7 (CH_), 122.3 (Cq), 109.1 (CH2_), 64.1 (CH2\N), 62.2 (CH2\N),
41.3 (\CH\), 31.4 (\CH2\), 28.3 (\CH2\), 28.2 (\CH2\), 22.9
(\CH2\), 20.5 (\CH3); MS, m/z: 205 (M+, 100).
2.14. N,N-diethyl-3,7-dimethylocta-2,6-dien-1-amine 8c
1H NMR: δ 5.32 (1H, t, J=6.8 Hz), 5.12 (1H, t, J=6.7 Hz), 2.83 (2H,
d, J=6.7 Hz), 2.61 (4H, q, J=7.13), 2 (2H, m), 1.94 (2H, m), 1.68 (3H, s),

48
B. Boualy et al. / Catalysis Communications 19 (2012) 46–50
Table 2
Effect of base on the allylic amination of 1.a
c
Entry
Catalyst/base
Time (h)
Conversionb (%)
Yield (%)
12
13
14
15
CuCl2/K2CO3
CuCl2/NEt3
Cu(OTf)2/K2CO3
Cu(OTf)2/NEt3
24
18
16
12
100
100
100
100
94
93
96
97
a
Conditions: Allylic chloride (0.5 mmol), catalyst (0.005 mmol), morpholine
(1 mmol), water (25 mL), K2CO3 or NEt3 (0.25 mmol), room temperature.
Scheme 1. Allylic amination of styrene chloride 1.
b
Determined by GC.
c
Isolated yield.
1.62 (3H, s), 1.50 (3H, s), 0.92 (6H, t, J=7.13); 13C NMR: δ 139.7 (Cq),
133.9 (Cq), 124.2 (CH_), 121.9 (CH_), 52.3 (CH2\N), 48.0 (CH2\N),
26.4 (\CH2\); 23.7 (\CH2\), 19.3 (\CH3), 16.7 (\CH3), 15.3
(\CH3); MS, m/z: 209 (M+, 100).
3. Results and discussion
Initially attempted was the allylic amination of (1-Chloromethyl-
vinyl)-benzene (styrene chloride) 1 chosen as model substrate under
conventional thermal conditions (Scheme 1). Systematic investigations
of its reactivity with morpholine as secondary amine, in the presence of
various copper based catalytic systems and solvents were undertaken
to define the best reaction conditions. The results are summarized in
Table 1.
In THF the reaction occurs either with CuCl2 or Cu(OTf)2, resulted
in a moderate yields of the allylic amine 2a (entries 2 and 3). Among
the other solvent studied, water was found to be the solvent of choice
(entries 4 and 5). All attempts to convert 1 into allylic amine 2a in the
absence of catalyst were unsuccessful even after prolonged reaction
times (entry 1). As shown in Table 1, Cu(OTf)2 seems to be more re-
active than CuCl2.
2.15. 1-(5-Isopropenyl-2-methylcyclohex-2-enyl)pyrrolidine 10a
[α]D20 =0 (c=1.5, CHCl3); 1H NMR: δ 5.6 (1H, m), 4.8 (2H, m), 2.9
(1H, m), 2.6 (4H, m), 2.15 (1H, m), 2.05 (2H, m), 1.9 (2H, m), 1.8 (4H,
m), 1.6 (3H, s), 1.5 (3H, s); 13C NMR: δ 150.2 (Cq), 143.2 (CH_), 124.4
(Cq), 109.5 (CH2_), 62.5 (CH\N), 54.8 (CH2\N), 37.8 (\CH\), 31.2
(\CH2\), 30.6 (\CH2\), 23.7 (\CH2\), 22.3 (\CH3), 20.8 (\CH3);
MS, m/z: 205 (M+, 100).
2.16. 4-(5-Isopropenyl-2-methylcyclohex-2-enyl)morpholine 10b
Next we investigate the effect of the addition of acceptor bases.
With 0.5 equivalent of K2CO3 or triethylamine, the reaction time
was reduced and the total conversion was obtained both with CuCl2
or Cu(OTf)2 (Table 2).
The extension of the allylic amination of 1 in water in the presence
of copper (II) complexes using pyrrolidine and diethylamine lead to
the allylated amines 2b and 2c in excellent yield 94%, 98% respectively
(Fig. 1).
[α]D20 =0 (c=1.7, CHCl3); 1H NMR: δ 5.5 (1H, m), 4.8 (2H, m), 3.4 (4H,
m), 3.1 (1H, m), 2.6 (4H, m), 2.15 (1H, m), 2.05 (2H, m), 1.9 (2H, m), 1.6
(3H, s), 1.5 (3H, s); 13C NMR: δ 150.2 (Cq), 143.2 (CH_), 124.4 (Cq),
110.5 (CH2_), 66.7 (O\CH2\), 63.5 (\CH\N), 56.8 (N\CH2\), 37.8
(\CH\), 31.2 (\CH2\), 30.6 (\CH2\), 22.3 (\CH3), 20.8 (\CH3);
MS, m/z: 221 (M+, 100).
Under identical mild reaction conditions, allylic amination was
carried out starting from terpenic chlorides (3, 5, 7 and 9) in the pres-
ence of Cu(OTf)2 as catalyst using pyrrolidine, morpholine and
diethylamine as a nitrogen-fragment donor. The reaction proceeds
smoothly at room temperature for 12 h in the presence of 0.5 equiv-
alent of triethylamine as the acceptor base. All the substrates are
converted regioselectively to the corresponding allylic amines in ex-
cellent yields. The results are depicted in Table 3.
Perillyl chloride 3, 5 and geranyl chloride 7 show a total conver-
sion even with pyrrolidine, morpholine and diethylamine. The best
yields were obtained with pyrrolidine. Carvyl chloride 9, prepared
according to the literature [28], as a secondary chloride was less effi-
cient than 3, 5 and 7 (entries 10–12). Comparing to the regiochemis-
try of the attack by various amines with allylic system in the presence
of nickel [29] and palladium [27] catalysts leads always to terminal
attack, the copper promoted amination of terpenic chlorides is
found to give the same results.
2.17. N,N-diethyl-2-methyl-5-(prop-1-en-2-yl)cyclohex-2-enamine 10c
[α]D20 =0 (c=1.5, CHCl3); 1H NMR: δ 5.4 (1H, m), 4.8 (2H, m), 2.9
(1H, m), 2.4 (4H, q, J=7.2), 2.15 (1H, m), 2.05 (2H, m), 1.9 (2H, m), 1.6
(3H, s), 1.5 (3H, s), 1.1 (6H, t, J=7.2); 13C NMR: δ 149.2 (Cq), 142.2
(CH_), 124.4 (Cq), 109.5 (CH2_), 62.5 (CH\N), 49.8 (CH2\N), 37.8
(\CH\), 31.2 (\CH2\), 30.6 (\CH2\), 22.7 (\CH3), 22.3 (\CH3),
14.8 (\CH3); MS, m/z: 207 (M+, 100).
Table 1
Effect of catalyst and solvent on the allylic amination of 1.a
Entry
Solvent
Catalyst
Time (h)
Conversionb (%)
Yieldc (%)
1
2
3
4
5
6
7
8
H2O
THF
THF
H2O
None
CuCl2
Cu(Otf)2
CuCl2
Cu(Otf)2
CuCl2
Cu(Otf)2
CuCl2
Cu(Otf)2
CuCl2
72
48
24
48
24
48
24
48
24
48
24
0
49
66
96
100
72
77
63
71
47
64
0
35
63
93
97
70
75
53
68
42
59
Cu(Otf)2
CuCl2
100
90
80
70
60
50
H2O
Dioxane
Dioxane
MeOH
MeOH
MeCN
MeCN
9
10
11
Cu(Otf)2
a
Conditions: Allylic chloride (0.5 mmol), catalyst (0.005 mmol), morpholine
(1 mmol), solvent (25 mL), room temperature.
pyrolidine Morpholine diethylamine
b
Determined by GC.
Isolated yield.
c
Fig. 1. Effect of secondary amine on the allylic amination of 1.

B. Boualy et al. / Catalysis Communications 19 (2012) 46–50
49
Table 3
Allylic amination of terpenic allylic chlorides.a
Entry
1
Allylic chloride
Secondary amine
Allylic amine
[α]D20 (concentration)
−13.3 (2.03)
Conversionb/Yieldc
100/98
Ref
[25]
2
3
4
−21.1 (1.78)
−9.3 (1.85)
−57.4 (1.93)
100/96
100/92
100/98
[25]
–
[32]
5
100/96
–
−53.9 (1.82)
6
7
−55.2 (1.97)
100/97
100/93
–
–
[25]
8
–
100/91
[25]
9
–
100/91
87/83
–
10
0
[25]
[α]D20 =−32 (2.01)
11
0
0
88/81
82/76
[25]
12
–
a
Conditions: Allylic chloride 0.5 mmol; Cu(OTf)2 0.05 mmol; secondary amine 1 mmol; K2CO3 0.25 mmol; water 15 ml; room temperature for 12 h.
Determined by GC.
Isolated yield.
b
c

50
B. Boualy et al. / Catalysis Communications 19 (2012) 46–50
[6] G.A. Hogan, A.A. Gallo, K.M. Nicholas, R.S. Srivastava, Tetrahedron Letters 43
It is also noteworthy that the β, γ-unsaturated amines synthesized
(2002) 9505–9508.
from optically active allylic chlorides 3 and 5 preserved an optical ac-
tivity as indicated in Table 3 (entries 1–6). In contrast allylic amines
derived from the optically active carvyl chloride 9 (Table 3, entries
10–12), was found optically inactive. As the mechanism of the reac-
tion is not yet perfectly clear, we can reasonably propose that the
amines 10a–10c derive from a symmetrical intermediate unlike the
4a–4c and 6a–6c compounds [30]. Hence, the reaction proceeds prob-
ably via an intermediate in which copper is linked to olefins through a
π-olefin bond [31], which can be converted to a symmetrical interme-
diate as we have previously shown with palladium complexes [30].
[7] G.S. Silverman, S. Strickland, K.M. Nicholas, Organometallics 5 (1986) 2117–2124.
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4. Conclusion
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