Stereoselective synthesis of allylamines by iron-catalyzed cross-coupling of 3-chloroprop-2-en-1-amines with grignard reagents. Synthesis of naftifine

Article abstract of DOI:10.1134/S1070428014030038

A general procedure for the synthesis of trans- and cis-allylamines has been developed on the basis of iron-catalyzed cross-coupling of Grignard reagents with stereochemically pure 3-chloroprop-2-en-1-amines prepared by allylation of amines with commercially available 1,3-dichloropropene isomers.

Full text of DOI:10.1134/S1070428014030038

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2014, Vol. 50, No. 3, pp. 322–331. © Pleiades Publishing, Ltd., 2014.
Original Russian Text © R.N. Shakhmaev, A.Sh. Sunagatullina, V.V. Zorin, 2014, published in Zhurnal Organicheskoi Khimii, 2014, Vol. 50, No. 3,
pp. 334–342.
Stereoselective Synthesis of Allylamines by Iron-Catalyzed
Cross-Coupling of 3-Chloroprop-2-en-1-amines with Grignard
Reagents. Synthesis of Naftifine
R. N. Shakhmaev, A. Sh. Sunagatullina, and V. V. Zorin
Ufa State Petroleum Technological University, ul. Kosmonavtov 1, Ufa, 450062 Bashkortostan, Russia
e-mail: biochem@rusoil.net
Received July 31, 2013
Abstract—A general procedure for the synthesis of trans- and cis-allylamines has been developed on the basis
of iron-catalyzed cross-coupling of Grignard reagents with stereochemically pure 3-chloroprop-2-en-1-amines
prepared by allylation of amines with commercially available 1,3-dichloropropene isomers.
DOI: 10.1134/S1070428014030038
Persistent interest in the development of new and
optimization of existing methods of synthesis of allyl-
amines is determined by their occurrence in nature and
wide application in medicine. Allylamine fragment is
a structural unit of many alkaloids, such as strychnine,
brucine, diaboline [1], tabersonine [2], and aloperine
[3], cytosinine [4], gabaculine [5], valienamine [6],
and other natural compounds. Allylamines are used in
the synthesis of amino acids [7], alkaloids [8], amino
sugars [9], and other biologically active compounds.
Commercial allylamine-based medicines, in particular
terbinafine [10] and naftifine [11] are of great practical
importance as antifungal drugs used in the treatment of
various mycoses.
Among a wide variety of known methods of syn-
thesis of allylamines, the main ones are based on nu-
cleophilic allylic substitution, electrophilic amination
of alkenes, sigmatropic rearrangements, and CH-ac-
tivation methods (for detailed reviews, see [12]).
However, procedures ensuring stereoselective syn-
thesis of allylamines with a required double bond
configuration are very few in number. Multicomponent
Petasis reaction [13] of (E)-vinylboronic acids or esters
with amines and aldehydes is stereospecific, but its
application is limited because of low accessibility of
(E)-vinylboronic acids and their esters; furthermore,
this reaction yields only trans-allylamines.
cene chlorides (prepared by hydrozirconation of
alkynes with the Schwartz reagent) with imines in the
presence of a catalytic amount of Ru(I) [15], as well as
by reactions of organozinc [16] and organoaluminum
derivatives [17] of alkenylzirconocene chlorides with
imines.
Heck arylation of allylamines under conventional
conditions generally yields mixture of regioisomers
[18]; if the reaction is carried out with aryl trifluoro-
methanesulfonates in the presence of bidentate ligands,
the β-position of allylamine is typically involved [19].
Examples of coupling of arenediazonium salts with
protected allylamines with formation of γ-substituted
products with fairly high regioselectivity and (E)-ste-
reoselectivity have recently been reported [20]. Xie
et al. [21] recently described a novel synthetic ap-
proach to (E)-allylamines, based on Pd-catalyzed
vinylation of aminals with alkenes.
The main drawbacks of the above methods are the
use of difficultly accessible reagents and expensive
and toxic catalysts, as well as impossibility to obtain
(Z)-allylamines.
In the present study we made an attempt to syn-
thesize stereochemically pure (E)- and (Z)-allylamines
by cross-coupling of (E)- and (Z)-3-chloroprop-2-en-
1-amines with Grignard reagents. Initial (E)- and
(Z)-3-chloroprop-2-en-1-amines were prepared by
nucleophilic substitution of the allylic chlorine atom in
the corresponding individual 1,3-dichloropropene iso-
mers by the action of primary and secondary amines;
trans-Allylamines were also synthesized with high
stereoselectivity by coupling of zirconocene imine
complexes with alkynes [14] or of (E)-alkenylzircono-
322

STEREOSELECTIVE SYNTHESIS OF ALLYLAMINES
323
Scheme 1.
Catalyst, solvent
Cl
NEt2
NEt2
+ BuMgCl
Me
Ia
IIa
these reactions occurred with complete retention of the
double bond configuration [22]. The trans- and cis-
stereoisomers of 1,3-dichloropropene (large-scale by-
product in the manufacture of allyl chloride) are
characterized by strongly different boiling points, so
that the isomers can be effectively separated by
fractional distillation. Individual 1,3-dichloropropene
isomers possess allylic and vinylic chlorine atoms
exhibiting different reactivities and thus offer the
unique synthetic potential. The strategy involving
functionalization of 1,3-dichloropropene isomers at the
allylic position with, e.g. N- and C-centered nucleo-
philes and subsequent stereoselective cross-coupling at
the vinylic position seems to be quite promising for
the synthesis of stereochemically pure unsaturated
compounds [23].
has found limited synthetic applications, due mainly to
high sensitivity of many functional groups to highly
reactive organomagnesium compounds. In 1971,
Tamura and Kochi [25] reported on successful FeCl3-
catalyzed vinylation of Grignard reagents with vinyl
bromide. In 1998, Cahiez and Avedissian [26] essen-
tially improved the procedure for Fe-catalyzed cross-
coupling of vinyl halides with aliphatic Grignard com-
pounds by adding N-methylpyrrolidin-2-one (NMP) as
co-solvent. In recent years, various iron catalytic
systems have been proposed, which ensured successful
cross-coupling of alkylmagnesium halides with aryl
halides, p-toluenesulfonates, and trifluoromethanesul-
fonates [27, 28], of aromatic Grignard reagents with
alkyl halides [29], heteroaromatic halides [28, 30], and
vinyl halides [31], of alkenylmagnesium halides with
alkyl halides [32], and of alkynylmagnesium bromides
with vinyl bromides and trifluoromethanesulfonates
[33]. Undoubted advantages of Fe-catalyzed cross-
The well-known Kumada–Tamao–Corriu reaction
[24], i.e., cross-coupling of aryl(vinyl) halides with
Grignard reagents catalyzed by Pd and Ni complexes,
Table 1. Cross-coupling of (2E)-3-chloro-N,N-diethylprop-2-en-1-amine (Ia) with butylmagnesium chloridea
Run no.
Solvent
Amount of NMP, equiv Catalyst
Amount, mol % Reaction time, min Yield of IIa,b %
01
02
03
04
05
06
07
08
09
10
11
12
13
14
15
16
THF
Diglyme
THF
THF
THF
THF
THF
THF
THF
NMP
THF
THF
THF
THF
THF
THF
0–
0–
0.00.5
01
02
04
06
08
16
0–
06
06
06
06
0–
0–
Fe(acac)3
Fe(acac)3
Fe(acac)3
Fe(acac)3
Fe(acac)3
Fe(acac)3
Fe(acac)3
Fe(acac)3
Fe(acac)3
Fe(acac)3
Fe(acac)3
–
3
3
3
3
3
3
3
3
3
3
1
–
1
1
1
1
90
90
90
90
90
90
90
90
90
90
90
90
15
45
90
90
60
62
76
80
86
92
94
91
82
63
c93c
03
84
90
03
16
Fe(acac)3
Fe(acac)3
Pd(OAc)2
Pd(PPh3)4
a
Reaction conditions: Ia, 0.5 mmol; BuMgCl, 0.75 mmol (1 M solution in THF, 0.75 mL); solvent, 1 mL; the Grignard reagent was added
to a solution of Ia at 0°C, and the mixture was then stirred at room temperature for a required time.
According to the GLC data.
b
c
A similar yield was obtained with 0.65 mmol of BuMgCl.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 50 No. 3 2014

SHAKHMAEV et al.
Table 2. Iron-catalyzed cross-coupling of 3-chloroprop-2-en-1-amines I with Grignard reagentsa
324
Yield of II,c E/Z-Isomer
RMgHlg
BuMgCld
3-Chloroprop-2-en-1-amines Ib
Allylamines II
%
ratio
Cl
Cl
NEt2
NEt2
Me
Me
83
99:10
Ia
IIa
N
N
80
99:10
IIb
Ib
O
O
Cl
N
N
N
84
82
99:10
99:10
Me
Ic
IIc
Cl
Cl
N
Me
Me
Me
Id
IId
H
N
H
Ph
N
Ph
89
76
99:10
05:95
IIe
Ie
NEt2
NEt2
Cl
Cl
If
IIf
N
N
78
05:95
Me
Ig
IIg
O
O
N
N
N
N
80
74
89
05:95
05:95
97:30
Me
Me
Ph
Cl
Cl
Cl
IIh
Ih
Ii
IIi
PhMgBre
N
N
IIj
Ib
O
O
Cl
Cl
N
N
Ph
Ph
N
N
92
90
98:20
95:50
Ic
Id
IIk
IIl
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 50 No. 3 2014

STEREOSELECTIVE SYNTHESIS OF ALLYLAMINES
325
Table 2 (Contd.).
Yield of II,c E/Z-Isomer
RMgHlg
3-Chloroprop-2-en-1-amines Ib
Allylamines II
%
ratio
Me
N
Me
PhMgBre
92
97:30
23:77
Cl
Cl
Ph
Ph
Ph
N
Ph
Ij
IIm
N
N
80
Ig
IIn
O
O
N
N
N
N
82
87
18:82
14:86
Cl
Cl
Ph
Ph
Ih
Ii
IIo
IIp
a
Reaction conditions: 3-chloroprop-2-en-1-amine I, 1.3 mmol; THF, 2 mL; 20–25°C, 1.5 h.
Initial amines I contained 99% of the major isomer.
b
c
d
e
Yield of isolated product.
Fe(acac)3, 2%; NMP, 0.8 mL; BuMgCl, 1.7 mmol (1 M solution in THF, 1.7 mL).
Fe(acac)3, 1%; NMP, 0.1 mL; PhMgBr, 2.1 mmol (1 M solution in THF, 2.1 mL).
couplings are high reaction rates and low toxicity and
almost did not affect the yield of allylic amine IIa
within the experimental error (Table 1, run no. 11). The
process is characterized by a high rate, and the yield of
IIa reaches 84% in the first 15 min (Table 1, run
nos. 13, 14). The yield of (2E)-N,N-diethylhept-2-en-1-
amine (IIa) in the absence of a catalyst was as poor as
3% (Table 1, run no. 12). The use of palladium cata-
lysts (Kumada reaction) gave much worse results
(Table 1, run nos. 15, 16), presumably due to low
reactivity of vinyl chloride Ia in the rate-determining
step (oxidative addition to zero-valent palladium).
Under the optimal conditions thus determined
butylmagnesium chloride was brought into reactions
with various stereochemically pure E- and Z-isomeric
tertiary and secondary 3-chloroprop-2-en-1-amines Ia–
Ii (Table 2). The reactions with E isomers were stereo-
specific, and the corresponding trans-allylamines IIa–
IIe were formed in high yields; the yields of (Z)-al-
lylamines IIf–IIi were lower, and the stereoselectivity
was also lower (Z/E 95:5). In order to attain the maxi-
mum yield of 3-phenylprop-2-en-1-amines IIj–IIp in
the cross-couplings of 3-chloroprop-2-en-1-amines Ib–
Id and Ig–Ij with phenylmagnesium bromide, some-
what increased amount of PhMgBr was necessary, and
low cost of the catalyst.
The present study was aimed at searching for op-
timal catalytic system for the cross-coupling reaction
of 3-chloroprop-2-en-1-amines with Grignard com-
pounds. As model reaction we used cross-coupling of
(2E)-3-chloro-N,N-diethylprop-2-en-1-amine (Ia) with
butylmagnesium chloride (Scheme 1, Table 1). The
reaction catalyzed by 3 mol % of Fe(acac)3 in con-
ventional ether solvents (tetrahydrofuran or diglyme)
gave the corresponding cross-coupling product,
(2E)-N,N-diethylhept-2-en-1-amine (IIa) in 60–62%
yield (Table 1, run nos. 1, 2). When the reaction of the
same compounds was carried out in THF–NMP mix-
tures, the yield of amine IIa increased as the concen-
tration of NMP rose, and it attained its maximum value
in the presence of 6 equiv of NMP. Further raising the
NMP concentration led to reduction of the yield of IIa
(63% in pure NMP; Table 1, run nos. 3–10). The lower
yield of IIa at low NMP concentrations was deter-
mined by incomplete conversion of the substrate,
whereas high NMP concentration favored formation of
by-products in addition to incomplete conversion.
Reduction of the amount of Fe(acac)3 to 1 mol %
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 50 No. 3 2014

SHAKHMAEV et al.
326
Scheme 2.
Me
Me
N
NHMe
N
Cl
Ph
Cl
Cl
PhMgBr, 1% Fe(acac)3
THF, NMP, 20°C
K2CO3, MeCN
III
Ik
IIq
the amount of NMP was reduced to 1 equiv, though
these reactions afforded high yields even in the pres-
ence of a catalytic amount of NMP (0.02 equiv). In all
cases, the reaction mixtures contained a small amount
of biphenyl (product of Fe-catalyzed homocoupling of
PhMgBr) which can be readily separated by chroma-
tography. (E)-3-Phenylprop-2-en-1-amines IIj–IIm
were formed with an appreciably higher stereoselec-
tivity (E/Z 95:5 to 98:2), as compared to the cor-
responding Z isomers (Z/E 77:23 to 86 :14). The
stereoselectivity in the reactions with (Z)-allylamines
Ig–Ii, leading to amines IIn–IIp, also decreased with
increase in the steric size of the amine fragment.
Cross-coupling of a secondary amine, (2E)-N-benzyl-
3-chloroprop-2-en-1-amine (Ie), with butylmagnesium
chloride smoothly produced secondary allylamine IIe
in high yield.
On the basis of the described approach we have
developed an efficient procedure for the synthesis of
naftifine, (2E)-N-methyl-N-(naphthalen-1-ylmethyl)-3-
phenylprop-2-en-1-amine. Naftifine (commercial name
Exoderil) is a widely known antifungal drug which
is used for the treatment of various mycoses. The
cross-coupling of phenylmagnesium bromide with
(2E)-3-chloro-N-methyl-N-(naphthalen-1-ylmethyl)-
prop-2-en-1-amine (Ik) [prepared by allylation of
N-methyl(naphthalen-1-yl)methanamine (III) with
(E)-1,3-dichloropropene] in the presence of 1 mol % of
Fe(acac)3 in a mixture of THF with NMP gave
naftifine (IIq) in 89% yield with 98% stereoselectivity
(Scheme 2).
IIn–IIp. A reliable proof of steric configuration of
the synthesized allylamines is the downfield shift of
the allylic carbon signal of trans isomers by 4–5 ppm
relative to the corresponding signal of their cis
isomers.
In summary, we have developed a general proce-
dure for the synthesis of trans- and cis-allylamines via
iron-catalyzed cross-coupling of Grignard reagents
with stereochemically pure 3-chloroprop-2-en-1-
amines prepared by allylation of amines with com-
mercially available isomeric 1,3-dichloropropenes.
EXPERIMENTAL
The IR spectra were recorded from thin films on
a Shimadzu IR Prestige-21 spectrometer with Fourier
transform (10 most intense absorption bands are
given). The NMR spectra were measured from solu-
tions in CDCl3 on Bruker AM-300 (300.13 MHz for
1H and 75.47 MHz for 13C) and AV-500 instruments
1
(500.13 MHz for H and 125.76 MHz for 13C); the
chemical shifts were determined relative to TMS (1H)
or solvent signal (CDCl3, δC 77.0 ppm).
GC/MS analysis was performed on a Shimadzu
GCMS-QP2010S instrument (electron impact, 70 eV;
a.m.u. range 33–350; HP-1MS capillary column,
30 m×0.25 mm, film thickness 0.25 μm; injector tem-
perature 280°C, ion source temperature 200°C; oven
temperature programming from 50 to 300°C at a rate
of 10 deg/min; carrier gas helium, flow rate
1.1 mL/min); given are the molecular ion peak and
10 most abundant fragment ion peaks. The elemental
compositions were determined from the high-resolu-
tion mass spectra which were recorded on a Finnigan
MAT 95XP instrument.
Solutions of Grignard compounds in THF were
prepared as described in [34], and their concentration
was determined by acid–base titration [35] or by
titration with salicylaldehyde phenylhydrazone [36].
(E)- and (Z)-3-Chloroprop-2-en-1-amines Ia–Ij were
synthesized according to the procedures reported in
The structure, stereochemical purity, and double
bond configuration of the cross-coupling products
were confirmed by GLC analyses and IR, NMR, and
mass spectra. The only difference between the IR
spectra of the (E)- and (Z)-allylamines was the pres-
ence in the former of a strong absorption band in the
region 966–976 cm–1, which is typical of out-of-plane
bending vibrations of C–H bonds in disubstituted
trans-alkenes. The coupling constant for the vinylic
protons in (E)-3-phenylprop-2-en-1-amines IIj–IIm
was 15.8–15.9 Hz against 11.6–11.8 Hz for Z isomers
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 50 No. 3 2014

STEREOSELECTIVE SYNTHESIS OF ALLYLAMINES
327
1
[22]. N-Methyl(naphthalen-1-yl)methanamine hydro-
2806, 1683, 1454, 1121, 1005, 974, 867. H NMR
spectrum, δ, ppm: 0.89 t (3H, 7-H, J = 6.9 Hz), 1.23–
1.41 m (4H, 5-H, 6-H), 2.04 q (2H, 4-H, J = 6.6 Hz),
2.44 t (4H, CH2N, J = 4.5 Hz), 2.94 d (2H, 1-H, J =
6.3 Hz), 3.72 t (4H, CH2O, J = 4.5 Hz), 5.41–5.66 m
(2H, 2-H, 3-H). 13C NMR spectrum, δC, ppm: 13.79
(C7), 22.09 (C6), 31.24 and 31.93 (C4, C5), 53.28
(CH2N), 61.18 (C1), 66.76 (CH2O), 125.26 (C2),
135.32 (C3). Mass spectrum, m/z (Irel, %): 183 (6) [M]+,
126 (18), 110 (30), 100 (25), 96 (22), 87 (100), 86
(42), 56 (23), 55 (62), 42 (17), 41 (31). Found: m/z
183.1633 [M]+. C11H21NO. Calculated: M 183.1623.
chloride was commercial product (Sigma–Aldrich).
(2E)-N,N-Diethylhept-2-en-1-amine (IIa). A solu-
tion of 0.192 g (1.3 mmol) of (2E)-3-chloro-N,N-di-
ethylprop-2-en-1-amine (Ia) and 9.2 mg (2 mol %) of
Fe(acac)3 in a mixture of 2 mL of THF and 0.8 mL of
NMP was cooled to 0°C, 1.7 mL of a 1 M solution of
BuMgCl in THF was slowly added dropwise under
argon, and the mixture was stirred for 1.5 h at room
temperature. The mixture was treated with 1 mL of
water and 5 mL of diethyl ether, the organic layer was
separated, the aqueous layer was extracted with diethyl
ether (2×3 mL), and the extracts were combined with
the organic phase, washed with brine, dried over
Na2SO4, and concentrated. The product was isolated by
silica gel column chromatography using hexane–ethyl
acetate (9:1 to 3:1) as eluent. Yield 0.183 g (83%),
oily substance. IR spectrum, ν, cm–1: 2963, 2926,
2872, 2795, 1703, 1456, 1381, 1292, 1200, 970.
1H NMR spectrum, δ, ppm: 0.89 t (3H, 7-H, J = 7 Hz),
1.02 t (6H, CH3CH2N, J = 7.2 Hz), 1.30–1.36 m (4H,
5-H, 6-H), 2.03 q (2H, 4-H, J = 6.8 Hz), 2.52 q (4H,
CH2N, J = 7.2 Hz), 3.04 d (2H, 1-H, J = 6.3 Hz), 5.43–
5.62 m (2H, 2-H, 3-H). 13C NMR spectrum, δC, ppm:
11.57 (CH3CH2N), 13.87 (C7), 22.14 (C6), 31.43 and
32.03 (C4, C5), 46.35 (CH2N), 55.13 (C1), 126.73 (C2),
133.95 (C3). Mass spectrum, m/z (Irel, %): 169 (7) [M]+,
154 (31), 97 (14), 86 (33), 73 (21), 72 (14), 58 (100),
56 (17), 55 (82), 42 (12), 41 (18). Found: m/z 169.1822
[M]+. C11H23N. Calculated: M 169.1830.
1-[(2E)-Hept-2-en-1-yl]pyrrolidine (IId) was syn-
thesized from amine Id. Yield 0.178 g (82%), oily
substance. IR spectrum, ν, cm–1: 2958, 2926, 2872,
1
2783, 1699, 1458, 1377, 1346, 1144, 970. H NMR
spectrum, δ, ppm: 0.89 t (3H, 7-H, J = 7 Hz), 1.26–
1.39 m (4H, 5-H, 6-H), 1.72–1.80 m (4H, 3′-H, 4′-H),
2.02 q (2H, 4-H, J = 6.7 Hz), 2.44–2.54 m (4H, 2′-H,
5′-H), 3.02 d (2H, 1-H, J = 6.6 Hz), 5.46–5.59 m (2H,
2-H, 3-H). 13C NMR spectrum, δC, ppm: 13.82 (C7),
22.09 (C6), 23.29 (C3′, C4′), 31.32 and 31.92 (C4, C5),
53.75 (C2′, C5′), 58.22 (C1), 127.27 (C2), 133.32 (C3).
Mass spectrum, m/z (Irel, %): 167 (14) [M]+, 166 (25),
124 (27), 110 (62), 84 (90), 71 (76), 70 (100), 55 (46),
43 (19), 42 (33), 41 (32). Found: m/z 167.1663 [M]+.
C11H21N. Calculated: M 167.1674.
(2E)-N-Benzylhept-2-en-1-amine (IIe) was syn-
thesized from amine Ie. Yield 0.234 g (89%), oily
substance. IR spectrum, ν, cm–1: 2957, 2926, 2872,
2857, 1480, 1454, 1120, 970, 733, 698. 1H NMR spec-
trum, δ, ppm: 0.89 t (3H, 7-H, J = 7 Hz), 1.25–1.38 m
(4H, 5-H, 6-H), 1.46 br.s (1H, NH), 2.03 q (2H, 4-H,
J = 6.5 Hz), 3.21 d (2H, 1-H, J = 6.4 Hz), 3.77 s (2H,
PhCH2), 5.48–5.63 m (2H, 2-H, 3-H), 7.21–7.35 m
(5H, Harom). 13C NMR spectrum, δC, ppm: 13.84 (C7),
22.11 (C6), 31.37 and 31.97 (C4, C5), 51.08 (C1), 53.18
(PhCH2), 126.79 (C2), 127.99 (CHarom), 128.11 (2C,
CHarom), 128.29 (2C, CHarom), 132.94 (C3), 140.31
(Carom). Mass spectrum, m/z (Irel, %): 203 (3) [M]+, 146
(12), 108 (23), 106 (24), 92 (11), 91 (100), 81 (8), 65
(10), 55 (12), 54 (9), 41 (10).
Compounds IIb–IIi were synthesized in a similar
way.
1-[(2E)-Hept-2-en-1-yl]piperidine (IIb) was syn-
thesized from amine Ib. Yield 0.189 g (80%), oily
substance. IR spectrum, ν, cm–1: 2932, 2853, 2793,
1
2752, 1466, 1454, 1155, 1119, 1107, 972. H NMR
spectrum, δ, ppm: 0.89 t (3H, 7-H, J = 7 Hz), 1.23–
1.65 m (10H, 5-H, 6-H, 3′-H, 4′-H, 5′-H), 2.03 q (2H,
4-H, J = 6.7 Hz), 2.35 br.s (4H, 2′-H, 6′-H), 2.89 d
(2H, 1-H, J = 6.6 Hz), 5.44–5.61 m (2H, 2-H, 3-H).
13C NMR spectrum, δC, ppm: 13.80 (C7), 22.12 (C6),
24.34 (C4′), 25.87 (C3′, C5′), 31.32 and 31.95 (C4, C5),
54.30 (C2′, C6′), 61.69 (C1), 126.54 (C2), 134.09 (C3).
Mass spectrum, m/z (Irel, %): 181 (11) [M]+, 180 (20),
138 (15), 124 (33), 110 (14), 98 (67), 85 (90), 84
(100), 55 (50), 42 (20), 41 (32). Found: m/z 181.1835
[M]+. C12H23N. Calculated: M 181.1830.
(2Z)-N,N-Diethylhept-2-en-1-amine (IIf) was
synthesized from amine If. Yield 0.167 g (76%), oily
substance. IR spectrum, ν, cm–1: 2960, 2930, 2873,
1
2797, 1685, 1466, 1382, 1200, 1168, 1068. H NMR
spectrum, δ, ppm: 0.90 t (3H, 7-H, J = 7 Hz), 1.04 t
(6H, CH3CH2N, J = 7.1 Hz), 1.31–1.36 m (4H, 5-H,
6-H), 2.07 q (2H, 4-H, J = 6.8 Hz), 2.52 q (4H, CH2N,
J = 7.1 Hz), 3.11 d (2H, 1-H, J = 6.4 Hz), 5.44–5.55 m
4-[(2E)-Hept-2-en-1-yl]morpholine (IIc) was syn-
thesized from amine Ic. Yield 0.201 g (84%), oily
substance. IR spectrum, ν, cm–1: 2958, 2927, 2855,
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SHAKHMAEV et al.
328
(2H, 2-H, 3-H). 13C NMR spectrum, δC, ppm: 11.71
(CH3CH2N), 13.93 (C7), 22.29 (C6), 27.18 (C4), 31.80
(C5), 46.62 (CH2N), 49.51 (C1), 126.59 (C2), 132.50
(C3). Mass spectrum, m/z (Irel, %): 169 (4) [M]+, 154
(14), 86 (19), 73 (25), 72 (13), 58 (100), 56 (10), 55
(45), 43 (5), 42 (8), 41 (12). Found: m/z 169.1825
[M]+. C11H23N. Calculated: M 169.1830.
prop-2-en-1-yl]piperidine (Ib) and 4.6 mg (1 mol %)
of Fe(acac)3 in a mixture of 2 mL THF and 0.1 mL of
NMP was cooled to 0°C, 2.1 mL of a 1 M solution of
PhMgBr in THF was slowly added dropwise under
argon, and the mixture was stirred for 1.5 h at room
temperature. The mixture was treated with 1 mL of
water and 5 mL of diethyl ether, the organic layer was
separated, and the aqueous layer was extracted with
diethyl ether (2×3 mL). The extracts were combined
with the organic phase, washed with brine, dried over
Na2SO4, and concentrated, and the residue was sub-
jected to silica gel column chromatography using
hexane–ethyl acetate (9:1 to 3:1) as eluent. Yield
0.232 g (89%), oily substance. IR spectrum, ν, cm–1:
2934, 2853, 2794, 2755, 1443, 1154, 1111, 966, 738,
1-[(2Z)-Hept-2-en-1-yl]piperidine (IIg) was syn-
thesized from amine Ig. Yield 0.183 g (78%), oily
substance. IR spectrum, ν, cm–1: 2931, 2855, 2778,
1
2745, 1466, 1452, 1298, 1153, 1117, 1107. H NMR
spectrum, δ, ppm: 0.90 t (3H, 7-H, J = 7 Hz), 1.24–
1.65 m (10H, 5-H, 6-H, 3′-H, 4′-H, 5′-H), 2.05 q (2H,
4-H, J = 6.7 Hz), 2.38 br.s (4H, 2′-H, 6′-H), 2.97 d
(2H, 1-H, J = 6.6 Hz), 5.43–5.60 m (2H, 2-H, 3-H).
13C NMR spectrum, δC, ppm: 13.91 (C7), 22.27 (C6),
24.31 (C4′), 25.92 (C3′, C5′), 27.12 (C4), 31.71 (C5),
54.47 (C2′, C6′), 55.85 (C1), 126.34 (C2), 132.75 (C3).
Mass spectrum, m/z (Irel, %): 181 (5) [M]+, 124 (9), 98
(22), 86 (8), 85 (67), 84 (100), 55 (22), 44 (10), 43 (7),
42 (12), 41 (19).
1
692. H NMR spectrum, δ, ppm: 1.37–1.70 m (6H,
3′-H, 4′-H, 5′-H), 2.43 br.s (4H, 2′-H, 6′-H), 3.11 d
(2H, 1-H, J = 6.6 Hz), 6.30 d.t (1H, 2-H, Jtrans = 15.9,
6.6 Hz), 6.49 d (1H, 3-H, Jtrans = 15.9 Hz), 7.18–
7.45 m (5H, Harom). 13C NMR spectrum, δC, ppm:
24.21 (C4′), 25.86 (C3′, C5′), 54.47 (C2′, C6′), 61.75 (C1),
126.16 (2C, CHarom), 127.12 (C2), 127.24 (CHarom),
128.41 (2C, CHarom), 132.52 (C3), 136.98 (Carom). Mass
spectrum, m/z (Irel, %): 201 (14) [M]+, 200 (14), 117
(44), 115 (31), 110 (100), 98 (21), 91 (16), 84 (13), 55
(9), 42 (12), 41 (12). Found: m/z 201.1524 [M]+.
C14H19N. Calculated: M 201.1517.
4-[(2Z)-Hept-2-en-1-yl]morpholine (IIh) was syn-
thesized from amine Ih. Yield 0.191 g (80%), oily
substance. IR spectrum, ν, cm–1: 2958, 2929, 2856,
1
2802, 1685, 1455, 1292, 1119, 1008, 866. H NMR
spectrum, δ, ppm: 0.90 t (3H, 7-H, J = 7 Hz), 1.25–
1.41 m (4H, 5-H, 6-H), 2.07 q (2H, 4-H, J = 6.7 Hz),
2.46 t (4H, CH2N, J = 4.5 Hz), 3.01 d (2H, 1-H, J =
6.4 Hz), 3.72 t (4H, CH2O, J = 4.5 Hz) 5.40–5.62 m
(2H, 2-H, 3-H). 13C NMR spectrum, δC, ppm: 13.87
(C7), 22.22 (C6), 27.13 (C4), 31.61 (C5), 53.51 (CH2N),
55.38 (C1), 66.90 (CH2O), 125.13 (C2), 133.79 (C3).
Mass spectrum, m/z (Irel, %): 183 (4) [M]+, 110 (13),
100 (12), 87 (100), 86 (48), 57 (40), 56 (15), 55 (34),
54 (17), 42 (12), 41 (22).
Compounds IIk–IIq were synthesized in a similar
way.
4-[(2E)-3-Phenylprop-2-en-1-yl]morpholine (IIk)
was synthesized from amine Ic. Yield 0.243 g (92%),
oily substance. IR spectrum, ν, cm–1: 2957, 2854,
1
2806, 1452, 1118, 1007, 968, 869, 740, 693. H NMR
spectrum, δ, ppm: 2.49 t (4H, CH2N, J = 4.6 Hz),
3.14 d (2H, 1-H, J = 6.8 Hz), 3.73 t (4H, CH2O, J =
4.6 Hz), 6.25 d.t (1H, 2-H, Jtrans = 15.8, 6.8 Hz), 6.53 d
(1H, 3-H, Jtrans = 15.8 Hz), 7.19–7.45 m (5H, Harom).
13C NMR spectrum, δC, ppm: 53.54 (CH2N), 61.30
(C1), 66.81 (CH2O), 125.92 (C2), 126.19 (2C, CHarom),
127.42 (CHarom), 128.44 (2C, CHarom), 133.23 (C3),
136.68 (Carom). Mass spectrum, m/z (Irel, %): 203 (23)
[M]+, 144 (12), 118 (13), 117 (67), 116 (11), 115
(45), 112 (100), 104 (11), 91 (23), 86 (16), 56 (34).
Found: m/z 203.1321 [M]+. C13H17NO. Calculated:
M 203.1310.
1-[(2Z)-Hept-2-en-1-yl]pyrrolidine (IIi) was syn-
thesized from amine Ii. Yield 0.162 g (74%), oily
substance. IR spectrum, ν, cm–1: 2959, 2927, 2873,
1
2782, 1696, 1460, 1378, 1345, 1199, 1141. H NMR
spectrum, δ, ppm: 0.90 t (3H, 7-H, J = 7 Hz), 1.26–
1.37 m (4H, 5-H, 6-H), 1.73–1.80 m (4H, 3′-H, 4′-H),
2.07 q (2H, 4-H, J = 6.6 Hz), 2.45–2.54 m (4H, 2′-H,
5′-H), 3.12 d (2H, 1-H, J = 6.6 Hz), 5.43–5.59 m (2H,
2-H, 3-H). 13C NMR spectrum, δC, ppm: 13.88 (C7),
22.24 (C6), 23.38 (C3′, C4′), 27.09 (C4), 31.68 (C5),
52.47 (C1), 53.96 (C2′, C5′), 126.88 (C2), 131.82 (C3).
Mass spectrum, m/z (Irel, %): 167 (6) [M]+, 110 (16), 84
(30), 72 (10), 71 (67), 70 (100), 55 (21), 54 (8), 43
(18), 42 (16), 41 (19).
1-[(2E)-3-Phenylprop-2-en-1-yl]pyrrolidine (IIl)
was synthesized from amine Id. Yield 0.218 g (90%),
oily substance. IR spectrum, ν, cm–1: 2965, 2874,
2785, 1690, 1497, 1346, 1140, 966, 739, 692. 1H NMR
spectrum, δ, ppm: 1.74–1.86 m (4H, 3′-H, 4′-H), 2.49–
2.60 m (4H, 2′-H, 5′-H), 3.26 d (2H, 1-H, J = 6.6 Hz),
1-[(2E)-3-Phenylprop-2-en-1-yl]piperidine (IIj).
A solution of 0.207 g (1.3 mmol) of 1-[(2E)-3-chloro-
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STEREOSELECTIVE SYNTHESIS OF ALLYLAMINES
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6.33 d.t (1H, 2-H, Jtrans = 15.8, 6.6 Hz), 6.53 d (1H,
3-H, Jtrans = 15.8 Hz), 7.18–7.46 m (5H, Harom).
13C NMR spectrum, δC, ppm: 23.38 (C3′, C4′), 54.00
(C2′, C5′), 58.33 (C1), 126.20 (2C, CHarom), 127.24 (C2),
127.70 (CHarom), 128.43 (2C, CHarom), 131.71 (C3),
137.05 (Carom). Mass spectrum, m/z (Irel, %): 187 (10)
[M]+, 186 (13), 117 (38), 115 (36), 110 (11), 96 (100),
91 (18), 84 (23), 44 (62), 42 (17), 40 (21).
(17) [M]+, 202 (12), 144 (14), 118 (13), 117 (65), 115
(43), 112 (100), 100 (14), 91 (24), 86 (16), 56 (25).
1-[(2Z)-3-Phenylprop-2-en-1-yl]pyrrolidine (IIp)
was synthesized from amine Ii. Yield 0.211 g (87%),
oily substance. IR spectrum, ν, cm–1: 2965, 2874,
2785, 1695, 1495, 1344, 1142, 773, 739, 700. 1H NMR
spectrum, δ, ppm: 1.73–1.86 m (4H, 3′-H, 4′-H), 2.47–
2.59 m (4H, 2′-H, 5′-H), 3.40 d (2H, 1-H, J = 6.4 Hz),
5.85 d.t (1H, 2-H, Jcis = 11.8, 6.4 Hz), 6.51 d (1H, 3-H,
Jcis = 11.8 Hz), 7.20–7.46 m (5H, Harom). 13C NMR
spectrum, δC, ppm: 23.40 (C3′, C4′), 53.89 (C1), 54.00
(C2′, C5′), 126.66 (CHarom), 127.99 (2C, CHarom), 128.82
(2C, CHarom), 129.97 (C2), 130.37 (C3), 137.13 (Carom).
Mass spectrum, m/z (Irel, %): 187 (8) [M]+, 186 (16),
117 (39), 115 (34), 110 (10), 96 (100), 91 (18), 84 (28),
70 (11), 44 (14), 42 (18).
(2E)-N-Benzyl-N-methyl-3-phenylprop-2-en-1-
amine (IIm) was synthesized from amine Ij. Yield
0.283 g (92%), oily substance. IR spectrum, ν, cm–1:
3026, 2785, 1495, 1451, 1365, 1024, 968, 736, 698,
1
693. H NMR spectrum, δ, ppm: 2.24 s (3H, CH3N),
3.19 d (2H, 1-H, J = 6.6 Hz), 3.55 s (2H, PhCH2),
6.31 d.t (1H, 2-H, Jtrans = 15.9, 6.6 Hz), 6.54 d (1H,
3-H, Jtrans = 15.9 Hz), 7.17–7.44 m (10H, Harom).
13C NMR spectrum, δC, ppm: 42.16 (CH3N), 59.81
(C1), 61.81 (PhCH2), 126.25 (2C, CHarom), 126.97 (C2),
127.33 (CHarom), 127.48 (CHarom), 128.23 (2C, CHarom),
128.49 (2C, CHarom), 129.09 (2C, CHarom), 132.57 (C3),
137.03 (Carom), 138.83 (Carom). Mass spectrum, m/z (Irel,
%): 237 (12) [M]+, 236 (8), 147 (10), 146 (88), 118 (9),
117 (43), 115 (29), 92 (11), 91 (100), 65 (14), 42 (68).
(2E)-N-Methyl-N-(naphthalen-1-ylmethyl)-3-
phenylprop-2-en-1-amine (IIq, naftifine) was syn-
thesized from amine Ik. Yield 0.332 g (89%), oily sub-
stance. IR spectrum, ν, cm–1: 2786, 1495, 1450, 1363,
1
967, 798, 792, 775, 744, 692. H NMR spectrum, δ,
ppm: 2.27 s (3H, CH3N), 3.28 d (2H, 1-H, J = 6.6 Hz),
3.94 s (2H, CH2N), 6.36 d.t (1H, 2-H, J = 15.8,
6.6 Hz), 6.58 d (1H, 3-H, J = 15.8 Hz), 7.21–7.55 m
(9H, Harom), 7.77 d (1H, Harom, J = 7.7 Hz), 7.84 d (1H,
Harom, J = 7.7 Hz), 8.30 d (1H, Harom, J = 7.9 Hz).
13C NMR spectrum, δC, ppm: 42.46 (CH3N), 60.05
(C1), 60.38 (CH2N), 124.60 (CHarom), 125.11 (CHarom),
125.55 (CHarom), 125.88 (CHarom), 126.30 (2C, CHarom),
127.35 (C2), 127.44 (CHarom), 127.53 (CHarom), 127.92
(CHarom), 128.43 (CHarom), 128.52 (2C, CHarom), 132.47
(Carom), 132.68 (C3), 133.88 (Carom), 134.81 (Carom),
137.12 (Carom). Mass spectrum, m/z (Irel, %): 287 (18)
[M]+, 196 (29), 182 (13), 146 (34), 142 (25), 141
(100), 117 (38), 116 (8), 115 (49), 91 (14), 42 (60).
Found: m/z 287.1686 [M]+. C21H21N. Calculated:
M 287.1674.
1-[(2Z)-3-Phenylprop-2-en-1-yl]piperidine (IIn)
was synthesized from amine Ig. Yield 0.209 g (80%),
oily substance. IR spectrum, ν, cm–1: 2933, 2853,
2781, 2745, 1443, 1298, 1153, 1113, 770, 698.
1H NMR spectrum, δ, ppm: 1.36–1.69 m (6H, 3′-H,
4′-H, 5′-H), 2.40 br.s (4H, 2′-H, 6′-H), 3.25 d (2H, 1-H,
J = 6.4 Hz), 5.82 d.t (1H, 2-H, Jcis = 11.6, 6.4 Hz),
6.55 d (1H, 3-H, Jcis = 11.6 Hz), 7.20–7.43 m (5H,
Harom). 13C NMR spectrum, δC, ppm: 24.21 (C4′), 25.91
(C3′, C5′), 54.61 (C2′, C6′), 57.02 (C1), 126.67 (CHarom),
128.02 (2C, CHarom), 128.83 (2C, CHarom), 130.18
(C2), 130.70 (C3), 137.19 (Carom). Mass spectrum,
m/z (Irel, %): 201 (11) [M]+, 200 (16), 118 (9), 117
(41), 115 (32), 110 (100), 98 (25), 91 (17), 84 (17), 42
(14), 41 (14).
4-[(2Z)-3-Phenylprop-2-en-1-yl]morpholine (IIo)
was synthesized from amine Ih. Yield 0.217 g (82%),
oily substance. IR spectrum, ν, cm–1: 2956, 2857,
2803, 1452, 1119, 1076, 1007, 783, 739, 700. 1H NMR
spectrum, δ, ppm: 2.45 t (4H, CH2N, J = 4.5 Hz),
3.27 d (2H, 1-H, J = 6.4 Hz), 3.71 t (4H, CH2O, J =
4.5 Hz), 5.77 d.t (1H, 2-H, Jcis = 11.8, 6.4 Hz), 6.59 d
(1H, 3-H, Jcis = 11.8 Hz), 7.18–7.45 m (5H, Harom).
13C NMR spectrum, δC, ppm: 53.57 (CH2N), 56.48
(C1), 66.87 (OCH2), 126.85 (CHarom), 128.05 (2C,
CHarom), 128.77 (2C, CHarom), 128.86 (C2), 131.59
(C3), 136.86 (Carom). Mass spectrum, m/z (Irel, %): 203
(2E)-3-Chloro-N-methyl-N-(naphthalen-1-yl-
methyl)prop-2-en-1-amine (Ik). N-Methyl(naphtha-
len-1-yl)methanamine (III), 1.71 g (0.01 mol), was
added to a suspension of 1.22 g (0.011 mol) of
(E)-1,3-dichloropropene and 2.07 g (0.015 mol) of
K2CO3 in 20 mL of anhydrous acetonitrile, and the
mixture was stirred for 1 h at room temperature and
was then heated for 4 h under reflux until complete
conversion of amine III (GLC). The mixture was
cooled and filtered, the precipitate was washed with
ethyl acetate, the filtrate was combined with the
washings and concentrated, and the product was
isolated by silica gel column chromatography using
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SHAKHMAEV et al.
330
10. Gupta, A.K. and Shear, N.H., J. Am. Acad. Dermatol.,
hexane–ethyl acetate (9:1 to 3:1) as eluent. Yield
1.97 g (80%), oily substance. IR spectrum, ν, cm–1:
2838, 2790, 1635, 1495, 1452, 1366, 1018, 934, 791,
1997, vol. 37, p. 979.
11. Monk, J.P. and Brogden, R.N., Drugs, 1991, vol. 42,
1
p. 659.
775. H NMR spectrum, δ, ppm: 2.21 s (3H, CH3N),
12. Cheikh, R.B., Chaabouni, R., Laurent, A., Mison, P.,
and Nafti, A., Synthesis, 1983, p. 685; Johannsen, M.
and Jørgensen, K.A., Chem. Rev., 1998, vol. 98,
p. 1689; Overman, L.E. and Carpenter, N.E., Org.
React., 2005, vol. 66, p. 1; Ramirez, T.A., Zhao, B., and
Shi, Y., Chem. Soc. Rev., 2012, vol. 41, p. 931.
13. Petasis, N.A. and Akritopoulou, I., Tetrahedron Lett.,
1993, vol. 34, p. 583; Candeias, N.R., Montalbano, F.,
Cal, P.M.S.D., and Gois, P.M.P., Chem. Rev., 2010,
vol. 110, p. 6169.
3.06 d (2H, 1-H, J = 6.3 Hz), 3.86 s (2H, CH2N),
6.04 d.t (1H, 2-H, Jtrans = 13.3, 6.3 Hz), 6.13 d (1H,
3-H, Jtrans = 13.3 Hz), 7.37–7.53 m (4H, Harom), 7.73–
7.84 m (2H, Harom), 8.23 d (1H, Harom, J = 7.9 Hz).
13C NMR spectrum, δC, ppm: 42.07 (CH3N), 57.23
(C1), 59.81 (CH2N), 120.14 (C3), 124.48 (CHarom),
125.05 (CHarom), 125.62 (CHarom), 125.86 (CHarom),
127.33 (CHarom), 128.05 (CHarom), 128.40 (CHarom),
130.83 (C2), 132.36 (Carom), 133.83 (Carom), 134.40
(Carom). Mass spectrum, m/z (Irel, %): 247 (1) and 245
(3.5) [M]+, 142 (32), 141 (98), 118 (26), 115 (69), 106
(30), 104 (100), 82 (27), 77 (24), 75 (61), 42 (79).
14. Buchwald, S.L., Watson, B.T., Wannamaker, M.W., and
Dewan, J.C., J. Am. Chem. Soc., 1989, vol. 111, p. 4486.
15. Kakuuchi, A., Taguchi, T., and Hanzawa, Y., Tetra-
hedron Lett., 2003, vol. 44, p. 923.
This study was performed under financial support
by the Ministry of Education and Science of the
Russian Federation in the framework of the base part
of state contract no. 49.
16. Wipf, P., Kendall, C., and Stephenson, C.R.J., J. Am.
Chem. Soc., 2003, vol. 125, p. 761.
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Qingwei, W., Johnson, M., and Wipf, P., Org. Lett.,
2011, vol. 13, p. 2318.
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