α-Phenylselanyl imines: Preparation of β-phenylselanyl amines and original synthesis of allylaziridines

Article abstract of DOI:10.1016/j.tet.2004.10.065

Resorting to suitable methods, a wide variety of α-phenylselanyl imines 2-5 were prepared from α-phenylselanyl aldehydes and α-phenylselanyl ketones 1. These compounds were reduced to afford β-phenylselanyl amines 6-9. Our experimental conditions have lim

Full text of DOI:10.1016/j.tet.2004.10.065

Tetrahedron 61 (2005) 447–456
a-Phenylselanyl imines: preparation of b-phenylselanyl amines
and original synthesis of allylaziridines
*
Catherine Miniejew, Francis Outurquin and Xavier Pannecoucke
*
´
`
Universite et INSA de Rouen-IRCOF, UMR 6014 CNRS, 1 rue Tesniere, 76821 Mont Saint Aignan, France
Received 9 July 2004; revised 15 October 2004; accepted 21 October 2004
Available online 5 November 2004
Abstract—Resorting to suitable methods, a wide variety of a-phenylselanyl imines 2–5 were prepared from a-phenylselanyl aldehydes and
a-phenylselanyl ketones 1. These compounds were reduced to afford b-phenylselanyl amines 6–9. Our experimental conditions have limited
the well known deselenenylation side-reaction occurring with most hydrides. On the other hand, the reaction of a-phenylselanyl imines 2
with organometallics led to the expected addition products only in the case of allylated derivatives. Depending on the temperature, either
b-phenylselanyl amines 11 or unexpected allylaziridines 12 were recovered.
q 2004 Elsevier Ltd. All rights reserved.
1. Introduction
Indeed, using different bases (best one: tert-BuLi), we could
not avoid the formation of dialkylated products or
diselenenylated imines together with the desired imines I.
As the selenenylated imines I are difficult to purify, these
two methods yielded the desired products in rather low
yields were abandoned. We then focused our efforts on a
third pathway which consists in the synthesis of imines I
from a-phenylselanyl carbonyl compounds. In this paper,
we reported a study on the preparation of selenenylated
imines I from a-phenylselanyl aldehydes or ketones and their
direct transformations via reduction and organometallic
additions (Scheme 2), which comes to complete our
preliminary observations.4a
As illustrated by the large number of organoselenium
intermediates involved in natural product synthesis, the
selenium methodology offers useful synthetic tools to
organic chemists.1 Our laboratory is especially interested
in the applications of a-phenylselanyl carbonyl compounds
as valuable bifunctional synthons. During the course of our
work, a simple multigram-scale preparation of a-phenylse-
lanyl aldehydes and a-phenylselanyl ketones has been
developed.2a Obtention and applications of b-phenylselanyl
silyl enol ethers have next been reported.3 a-Phenylselanyl
imines are other pivotal targets which give access to
interesting nitrogen-containing compounds. However, they
seem to have been little studied.4
2. Synthesis of a-phenylselanyl imines
Preliminary studies on the various routes to access
a-phenylselanyl imines I have been performed, based on
the work on a-sulfanyl imines.5 By analogy with the sulfur
series, three methods were assayed to prepare selenenylated
imines I. Two of them were based on a metallation process
(Scheme 1), selenenylation of imines or alkylation of
a-phenylselanyl imines. Therefore, using LDA as base,
followed by addition of PhSeBr or PhSeSePh, imines
deriving from aldehydes or ketones could be transformed
into a-phenylselanyl imines I but in poor yields varying
from 20 (R4ZBn) to 60% (R4Ztert-Bu). The second
metallation procedure, based on the alkylation of a-phe-
phenylselanyl imines, revealed to be even more difficult.
The reactivity of a-phenylselanyl carbonyl compounds is
highly variable and depends particularly on the steric
hindrance at the a carbon. Thus, in each case, the best and
simplest experimental conditions were selected to convert
a-phenylselanyl aldehydes or ketones into imines. The
condensation of a-phenylselanyl ethanal 1a2a with benzyl-
amine was achieved in ether at K30 8C in the presence of
potassium hydroxide. Starting from aldehydes 1b–f,2a better
Keywords: Selenium; Aziridine; Imine.
* Corresponding authors. Tel.: C33 2 3552 2402; fax: C33 2 3553 2959;
e-mail addresses: francis.outurquin@univ-rouen.fr;
xavier.pannecoucke@insa-rouen.fr
Scheme 1.
0040–4020/$ - see front matter q 2004 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tet.2004.10.065

448
C. Miniejew et al. / Tetrahedron 61 (2005) 447–456
prepared just before use), but no purification (distillation,
chromatography) could be achieved due to decomposition.
However, the crude imines are pure enough for further
transformations. The a-phenylselanyl imines 2h–i are solids
which, after rinsing with hexane, gave satisfactory elemental
analysis. Only one set of signal in 1H NMR was observed for
imines 2a–i issued from aldehydes. According to literature
data,6 we assumed that the a-phenylselanyl aldimines adopt
the anti configuration. No tautomery was observed. Never-
theless, the enaminic form of the N-tert-butyl imine 5c could
be obtained after a prolonged heating in dichloromethane.
Scheme 2.
results were obtained in dichloromethane at room tempera-
ture in the presence of magnesium sulfate. The more
hindered aldehydes 1g–i,2b bearing a tertiary a carbon,
could also be converted into a-phenylselanyl imines 2g–i
either at reflux of toluene with a Dean–Stark apparatus or in
the presence of titanium tetrachloride and 4 equiv of amine.4
These latter conditions were the sole allowing access to
imines 2j–o from a-phenylselanyl ketones 1j–o.2a The use
of benzylamine allows further easy debenzylation to access
to primary amines. Nevertheless, our developed method-
ology can also be transposed to other amines as shown with
a-phenylselanyl imines 3c, 4c and 5c resulting from the
condensation of a-phenylselanyl butanal 1c with allyl-
amine, cyclohexylamine or tert-butylamine. The stability of
the imines increases with the hindrance of the amine or the
carbonyl substituents. Thus, a-phenylselanyl imines can be
kept at 0 8C under inert atmosphere (a few days for 2g–i, one
day for enolisable imines, while compound 2a should be
3. Reduction of a-phenylselanyl imines
The most important problem known to occur during the
reduction of imines 2–5, is the substrate’s deselenenylation
leading to the formation of deselenenylated amines. This
side-reaction results from a selenophilic attack of the
hydride as observed during the reduction of a-phenylselanyl
ketones.7 Indeed, treatment of a-phenylselanyl imines with
LiAlH4 led to a complete deselenenylation, even at low
temperatures. Among less reactive reducing agents (NaBH4,
Zn(BH4)2, BH3–THF, BH3–SMe2), only NaBH4 afforded
the desired b-phenylselanyl amines, but together with the
deselenenylated amines (15–20%) (Scheme 3, Table 1).
Scheme 3. (i) Method A: R4NH2 (1 equiv), KOH, Et2O, K30 8C, 2 h; Method B: R4NH2 (1 equiv), MgSO4, CH2Cl2, 20 8C, 4 h; Method C: R4NH2 (1 equiv),
toluene, reflux, 12 h; Method D, R4NH2 (4 equiv), TiCl4, Et2O, 20 8C, 4 h. (ii) NaBH3CN (0.5 equiv), AcOH, EtOH, K78 8C, 1 h.
Table 1. Synthesis of b-phenylselanyl amines 6–9 via imines 2–5 (Scheme 3)
Substrates
R1
R2
R3
R4
Method for imine
preparation
Products
Yielda (%) (syn/anti)
1a
1b
1c
H
Me
Et
H
H
H
H
H
H
Bn
Bn
Bn
Allyl
cC6H11
tert-Bu
Bn
Bn
Bn
Bn
Bn
Bn
Bn
Bn
Bn
Bn
Bn
A
B
B
B
6a
6b
6c
7c
8c
9c
6d
6e
6f
6g
6h
6i
6j
6k
6l
54
41
72
64
57
56
69
65
67
64
59
51
50
71
68
B
Bb
1d
1e
1f
1g
1h
1i
1j
1k
1l
iPr
Bu
Bn
Me
Ph
H
H
H
Me
Me
H
H
H
H
H
H
B
B
B
C or D
C or D
Cc or D
D
D
D
D
D
D
–(CH2)5–
H
H
H
Me
Me
H
H
H
H
H
H
Me
tert-Bu
Ph
Et
Ph
1m
1n
1o
6m
6n
6o
57 (80/20)
53 (100/0)
57 (80/20)
–(CH2)4–
Bn
a Estimated from 1.
b 12 h at reflux of CH2Cl2.
c 48 h at reflux of toluene.

C. Miniejew et al. / Tetrahedron 61 (2005) 447–456
449
4. Organometallic additions to a-phenylselanyl imines
In order to access to various other b-phenylselanyl amines,
we next studied organometallic additions on imines 2. After
numerous assays with lithium derivatives (MeLi, BuLi),
zinc derivatives (Et2Zn, BuZnCl), a copper derivative
(MeCu) and arylated or alkylated grignard reagents
(BnMgBr, VinylMgBr, PropylMgBr), only allylated mag-
nesium derivatives led to the expected addition products.
The use of crotyl magnesium showed that, in these cases, the
reaction proceed through a six-membered cyclic transition
state (Scheme 4). The addition of allylmagnesium chloride
to imines 2 was first achieved in mild experimental
conditions to avoid the substrate’s deselenenylation
(Scheme 5, Table 2).
Scheme 4. (i) CrotylMgCl (1.1 equiv), THF, K40/0 8C, 2 h.
At K40 8C, the reaction proceeded cleanly and led to
b-phenylselanyl amines 11 in 47–78% yield. However with
2h, the desired amine 11h was obtained as a mixture with
the unexpected allylaziridine 12h. Starting from 1m,
the aza-heterocycle 12m was even the sole product of the
reaction, along with diphenyldiselenide, coming from the
hydrolysis of PhSeMgBr. Such in situ cyclization has
already been observed during reduction or organometallic
additions to a-chloro imines.9 After considering different
reaction parameters, we realized that we could favor either
one or the other product by controlling the temperature.
Indeed, when the allylmagnesium additions were carried out
at reflux of THF, the allylaziridines 12 became the sole or
the major products of the reaction. Probably because of the
substrate’s hindrance, no addition product was observed
with the pinacolone derivative 1k. No allylaziridine has
been obtained from 1j even at higher temperature.
The best results were obtained with NaBH3CN at K78 8C in
the presence of acetic acid. These experimental conditions
avoided the formation of the deselenenylated amines and
afforded the b-phenylselanyl amines 6–9 in 41–72% yield.
It should be underlined that ketone 1m led to the
b-phenylselanyl amine 6m in 60% de while substrate 1n
afforded the sole syn diastereomer 6n. The stereochemistry
of products 6m,n was assigned after analysis of the
corresponding aziridines obtained after an internal SN2
displacement of the selanyl group.4a Such syn selectivity has
already been observed during the reduction of a-phenyl-
selanyl ketones.8 It can be rationalized by a Felkin–Ahn-
type model with a stereoelectronic controle by the selanyl
group.
Scheme 5. (i) allylMgCl (1.1 equiv), THF, K40/0 8C, 2 h. (ii) allylMgCl (1.1 equiv), THF, reflux, 2 h.
Table 2. Synthesis of homoallylic b-phenylselanyl amines 11 and allylaziridines 12 via imines 2 (Scheme 5)
Substrates
R1
R2
H
R3
T (8C)
11 Yielda (%) (syn/anti)
12 Yielda (%) (cis/trans)
1d
iPr
H
K40/0
65
K40/0
65
K40/0
65
K40/0
65
K40/0
65
K40/0
65
K40/0
65
K40/0
65
78 (55/45)
—
69 (100/0)
—
—
73 (55/45)
—
53 (100/0)
—
57
20 (0/100)
41 (0/100)
—
1e
1g
1h
1j
Bu
Me
Me
H
H
H
Me
Ph
H
H
74
11
H
47 (100/0)
18 (100/0)
58
Me
tBu
Ph
Et
52
—
b
1k
1l
H
H
—
b
—
65
H
H
—
61
—
—
—
1m
1n
Me
Me
H
61 (100/0)
57 (100/0)
—
H
Ph
K40/0
65
64 (100/0)
—
59 (0/100)
a Estimated from 1.
b Starting material recovered.

450
C. Miniejew et al. / Tetrahedron 61 (2005) 447–456
dichloromethane (50 ml). The mixture was stirred for
10 min at K5 8C and the amine (5 mmol) was added
dropwise. The whole was then stirred for 3 h at room
temperature. The magnesium sulfate was filtered, rinsed
with dichloromethane and the organic phase was concen-
trated. These a-phenylselanyl aldimines could be stored one
day at 0 8C under argon.
Scheme 6. (i) NBS (1.1 equiv), CH3CN, 20 8C, 5 min.
Nevertheless, the allylaziridine 12j could be synthesized
after activation of the selanyl group of 11j with N-
bromosuccinimide (Scheme 6).10 When the reaction product
exhibits two stereogenic centers, only one diastereomer was
obtained either for the b-phenylselanyl amines 11 or for the
allylaziridines 12 except for compounds 11d and 12d
derived from isovaleraldehyde. NOE experiments on
allylaziridines 12h, 12n and 12m allowed to assign the cis
stereochemistry to allylaziridines 12. We then deduced a syn
relationship between the amino and the selanyl group of the
corresponding b-phenylselanyl amines 11.
Procedure C: A solution of a-phenylselanyl aldehydes 1g–i
(5 mmol) and amine (5.25 mmol) in toluene (50 ml) was
heated for 12 h under reflux with elimination of water
(Dean–Stark). For 2i, the heating should be continued for
48 h. The solvent was eliminated under vacuo. The imines
2h and 2i crystallized slowly and were rinsed with hexane.
These a-phenylselanyl aldimines could be stored a few days
at 0 8C under argon.
Procedure D: Amine (20 mmol) was added to the a-
phenylselanyl carbonyl compounds 1g–n (5 mmol) in ether
(50 ml) at 0 8C, under argon. A solution of titanium
tetrachloride (708 mg, 3.75 mmol) in heptane (2 ml) was
then slowly introduced. The mixture was stirred for 30 min
at 0 8C and then for 3 h at room temperature. The titanium
salts were filtered and rinsed with ether.
In summary, we report convenient methods to convert
a-phenylselanyl aldehydesandketonesintothe corresponding
a-phenylselanyl imines 2–5. The reduction of these latter
with NaBH3CN led to b-phenylselanyl amines 6–9 without
deselenenylation of the substrates. On the other hand,
depending on the temperature, addition of allyl magnesium
chloride provided either b-phenylselanyl amines 11 or
allylaziridines 12. To our knowledge, this constitutes the
first synthesis of allylaziridines.
All the a-phenylselanyl imines 2–5 were isolated but not
purified because of decomposition. That is why for most of
1
them we just reported the H NMR spectra. For 2a–g IR
nC]NZ1640–1650 cmK1
.
5.1.1. Phenyl-N-(2-(phenylselanyl)ethylidene)methana-
mine 2a. H NMR d: 3.68 (d, 2H, JZ5.7 Hz, H-2), 4.54
(s, 2H, CH2Ph), 7.05–7.35 (m, 8H, Ph), 7.50–7.55 (m, 2H,
1
5. Experimental
THF was distilled over sodium/benzophenone and dichloro-
methane over P2O5. Ether was dried over sodium.
Ph), 7.78 (t, 1H, JZ5.7 Hz, H-1).
5.1.2. Phenyl-N-(2-(phenylselanyl)propylidene)methana-
mine 2b. H NMR d: 1.55 (d, 3H, JZ7.0 Hz, H-3), 3.71–
4.20 (m, 1H, H-2), 4.44 (d, 1H, JZ14.0 Hz, CH2Ph), 4.54
(d, 1H, JZ14.0 Hz, CH2Ph), 7.0–7.10 (m, 2H, Ph), 7.15–
7.35 (m, 6H, Ph), 7.45–7.60 (m, 2H, Ph), 7.71 (d, 1H, JZ
6.1 Hz, H-1).
1H NMR (300 MHz) and 13C NMR (75 MHz) spectra were
recorded on a Brucker DPX 300 instrument and carried out
in CDCl3. 77Se NMR spectra were recorded on a Bruker
DPX 400 spectrometer operating at 76.29 MHz for 77Se,
using as pulsed length 19 ms (908 pulseZ19 ms) and an
optimized relaxation delay of 2 s. An average of 1500 scans
for 77Se NMR was necessary to have reliable information.
Chemical shifts (d) are expressed in ppm relative to TMS for
1H and 13C nuclei and to Me2Se for 77Se nuclei; coupling
constants (J) are given in Hertz; coupling multiplicities are
reported using conventional abbreviations. Elemental ana-
lysis were obtained on a Carlo-Erba 1106 analysor and Mass
Spectra on a HP5890 (electronic impact 70 eV) using GC–
MS coupling with a Jeol AX 500.
1
5.1.3. Phenyl-N-(2-(phenylselanyl)butylidene)methana-
1
mine 2c. H NMR d: 1.06 (t, 3H, JZ7.3 Hz, H-4), 1.63–
2.10 (m, 2H, H-3), 3.84 (dt, 1H, JZ7.1, 7.1 Hz, H-2), 4.42
(d, 1H, JZ14.0 Hz, CH2Ph), 4.55 (d, 1H, JZ14.0 Hz,
CH2Ph), 7.00–7.05 (m, 2H, Ph), 7.10–7.30 (m, 6H, Ph),
7.45–7.52 (m, 2H, Ph), 7.64 (d, 1H, JZ7.1 Hz, H-1).
5.1.4. Phenyl-N-(3-methyl-2-(phenylselanyl)butylidene)
methanamine 2d.4a 1H NMR d: 1.11 (d, 3H, JZ6.7 Hz,
H-4), 1.18 (d, 3H, JZ6.7 Hz, H-4), 1.96–2.39 (m, 1H, H-3),
3.82 (dd, 1H, JZ7.8, 8.2 Hz, H-2), 4.40 (d, 1H, JZ13.9 Hz,
CH2Ph), 4.57 (d, 1H, JZ13.9 Hz, CH2Ph), 7.00–7.06 (m,
2H, Ph), 7.15–7.37 (m, 6H, Ph), 7.48–7.53 (m, 2H, Ph), 7.70
(d, 1H, JZ8.2 Hz, H-1).
5.1. Preparation of a-phenylselanyl imines 2–5
Procedure A: A solution of a-phenylselanyl ethanal 1a
(995 mg, 5 mmol) in ether (5 ml) was added dropwise at
K30 8C to the amine (5.5 mmol) in the same solvent
(30 ml). The mixture was stirred for 2 h at K30 8C before
adding KOH (1 g) and then stirred for 15 h at K5 8C. The
solution was filtered and concentrated. This a-phenylselanyl
aldimine should be used immediately after its preparation.
5.1.5. Phenyl-N-(2-(phenylselanyl)hexylidene)methana-
1
mine 2e. H NMR d: 0.82 (d, 3H, JZ7.2 Hz, H-6), 1.15–
1.48 (m, 4H, H-5, H-4), 1.67–1.82 (m, 2H, H-3), 3.80–3.85
(m, 1H, H-2), 4.34 (d, 1H, JZ14.1 Hz, CH2Ph), 4.47 (d, 1H,
JZ14.1 Hz, CH2Ph), 6.93–7.42 (m, 10H, Ph), 7.54 (d, 1H,
JZ7.7 Hz, H-1).
Procedure B: Magnesium sulfate (3 g) was added to a
solution of a-phenylselanyl aldehydes 1b–f (5 mmol) in

C. Miniejew et al. / Tetrahedron 61 (2005) 447–456
451
5.1.6. Phenyl-N-(3-phenyl-2-(phenylselanyl)propylidene)
methanamine 2f. 1H NMR d: 3.22–3.30 (m, 2H, H-3),
4.24–4.35 (m, 1H, H-2), 4.50 (s, 2H, CH2Ph), 6.95–7.05 (m,
2H, Ph), 7.20–7.40 (m, 11H, Ph), 7.55–7.60 (m, 2H, Ph),
7.75 (d, 1H, JZ6.8 Hz, H-1).
4.43 (s, 2H, CH2Ph), 7.04–7.24 (m, 8H, Ph) 7.45–7.52 (m,
2H, Ph). 13C NMR d: 23.2, 26.9, 34.7, 52.2 (C-2), 54.1
(CH2Ph), 126.5, 127.0, 128.4, 129.1, 129.6, 129.8, 134.8.
5.1.16. N-(2-(Phenylselanyl)butylidene)allylamine 3c. 1H
NMR d: 1.03 (t, 3H, JZ7.3 Hz, H-4), 1.60–2.03 (m, 2H,
H-3), 3.76 (dt, 1H, JZ7.2, 7.2 Hz, H-2), 3.85–3.95 (m, 2H,
CH2CH]CH2), 4.90–5.05 (m, 2H, CH2CH]CH2), 5.67–
5.75 (m, 1H, CH2CH]CH2), 7.20–7.30 (m, 2H, Ph),
7.45–7.65 (m, 4H, Ph, H-1).
5.1.7. Phenyl-N-(2-methyl-2-(phenylselanyl)propyli-
dene) methanamine 2g.4a 1H NMR d: 1.47 (s, 6H, H-3),
4.46 (s, 2H, CH2Ph), 7.04–7.38 (m, 10H, Ph), 7.69 (s, 1H,
H-1).
5.1.8. Phenyl-N-(2-phenyl-2-(phenylselanyl)propylidene)
5.1.17. N-(2-(Phenylselanyl)butylidene)cyclohexylamine
4c. 1H NMR d: 1.04 (t, 3H, JZ7.4 Hz, H-4), 1.05–1.87 (m,
12H, Cy, H-3), 2.79–2.87 (m, 1H, Cy), 3.78 (dt, 1H, JZ7.4,
7.4 Hz, H-2), 7.15–7.60 (m, 6H, Ph, H-1).
1
methanamine 2h. MpZ35 8C. IR nC]NZ1630 cmK1. H
NMR d: 1.87 (s, 3H, H-3), 4.56 (d, 2H, JZ14.1 Hz, CH2Ph),
4.66 (d, 2H, JZ14.1 Hz, CH2Ph), 7.07–7.42 (m, 15H, Ph),
8.16 (s, 1H, H-1). 13C NMR d: 24.9 (C-3), 55.1 (C-2), 63.8
(CH2Ph), 126.8, 127.1, 127.4, 127.8, 128.4, 128.6, 128.9,
129.1, 138.0, 139.1, 142.2 (Ph), 166.3 (C-1). Anal. Calcd for
C22H21NSe: C, 69.83; H, 5.59; N, 3.70. Found: C, 69.71; H,
5.39; N, 3.61.
5.1.18. N-(2-(Phenylselanyl)butylidene)tert-butylamine
1
5c. H NMR d: 1.04 (s, 9H, C(CH3)3), 1.08 (t, 3H, JZ
7.4 Hz, H-4), 1.54–2.02 (m, 2H, H-3), 3.85 (dt, 1H, JZ7.4,
7.4 Hz, H-2), 7.10–7.55 (m, 6H, Ph, H-1).
5.1.9. Phenyl-N-((1-(phenylselanyl)cyclohexyl)methyli-
dene) methanamine 2i. MpZ43 8C. IR nC]N
5.2. Reduction of a-phenylselanyl imines 2–5
Z
1
1625 cmK1. H NMR d: 1.25–2.05 (m, 10H, Cy), 4.53 (s,
To the a-phenylselanyl imines 2–5 (5 mmol) in ethanol
(60 ml) at K78 8C, under argon, were added successivelly
sodium cyanoborohydride (162 mg, 2.5 mmol) and acetic
acid (300 mg, 5 mmol). The reaction mixture was stirred for
1 h at K78 8C and quenched with water (70 ml). After
dichloromethane (100 ml) addition, the aqueous phase was
separated and washed with dichloromethane (2!80 ml).
The combined organic phases were dried over MgSO4 and
concentrated. The crude product was purified by silica gel
chromatography (cyclohexane/Et2O: 90/10).
2H, CH2Ph), 7.10–7.50 (m, 10H, Ph), 7.66 (s, 1H, H-1). 13
C
NMR d: 23.4, 25.7, 29.4, 34.0 (Cy), 54.8 (C-Se), 63.9
(CH2Ph), 126.4, 126.6, 127.7, 128.2, 128.3, 128.4, 128.5,
137.9 (Ph), 166.7 (C-1). Anal. Calcd for C20H23NSe: C,
67.40; H, 6.51; N, 3.93. Found: C, 67.34; H, 6.57; N, 3.85.
5.1.10. Phenyl-N-(1-(phenylselanyl)propan-2-ylidene)-
methan amine 2j.4a 1H NMR d: 1.98 (s, 3H, H-3), 3.69
(s, 2H, H-1), 4.33 (s, 2H, CH2Ph), 7.04–7.52 (m, 10H, Ph).
5.1.11. Phenyl-N-(3,3-dimethyl-1-(phenylselanyl)butan-
2-ylidene)methanamine 2k.4a Z/E: 85/15 (non assigned).
Major configuration: 1H NMR d: 1.16 (s, 9H, H-4), 3.64 (s,
2H, H-1), 4.52 (s, 2H, CH2Ph), 7.14–7.47 (m, 10H, Ph).
Minor configuration: 1H NMR d: 1.17 (s, 9H, H-4), 3.80 (s,
2H, H-1), 4.76 (s, 2H, CH2Ph), 7.14–7.47 (m, 10H, Ph).
5.2.1. N-Benzyl-2-(phenylselanyl)ethan-1-amine 6a.
Yield: 54%. H NMR d: 1.80 (sl, 1H, NH), 2.88–2.95 (m,
1
2H, H-2), 3.05–3.12 (m, 2H, H-1), 3.80 (s, 2H, CH2Ph),
7.22–7.36 (m, 8H, Ph), 7.47–7.55 (m, 2H, Ph). 13C NMR d:
28.5 (C-2), 48.2 (C-1), 53.3 (CH2Ph), 127.0, 127.7, 128.0,
128.4, 129.0, 131.4, 132.9, 140.1 (Ph). Anal. Calcd for
C15H17NSe: C, 62.06; H, 5.90; N, 4.82. Found: C, 62.33; H,
6.21; N, 4.59.
5.1.12. Phenyl-N-(1-phenyl-2-(phenylselanyl)ethylidene)
methanamine 2l. Z/E: 60/40 (non assigned). Major
configuration: H NMR d: 4.01 (s, 2H, H-2), 4.33 (s, 2H,
1
5.2.2. N-Benzyl-2-(phenylselanyl)propan-1-amine 6b.
Yield: 41%. Bp0.05: 121–122 8C. H NMR d: 1.52 (d, 3H,
1
1
CH2Ph), 6.99–7.50 (m, 15H, Ph). Minor configuration: H
NMR d: 4.03 (s, 2H, H-2), 4.48 (s, 2H, CH2Ph), 7.08–7.78
(m, 15H, Ph).
JZ6.7 Hz, H-3), 1.95 (sl, 1H, NH), 2.71–2.97 (m, 2H, H-1),
3.42–3.59 (m, 1H, H-2), 3.90 (s, 2H, CH2Ph), 7.25–7.45(m,
8H, Ph), 7.60–7.65(m, 2H, Ph). 13C NMR d: 20.3 (C-3), 40.0
(C-2), 53.3, 54.6 (C-1, CH2Ph), 126.7, 126.9, 127.4, 127.9,
128.2, 128.7, 135.2, 140.1 (Ph). Anal. Calcd for C16H19NSe:
C, 63.15; H, 6.29; N, 4.60. Found: C, 63.45; H, 6.35; N,
4.34.
5.1.13. Phenyl-N-(2-(phenylselanyl)pentan-3-ylidene)
methanamine 2m.4a 1H NMR d: 1.04 (t, 3H, JZ7.7 Hz,
H-5), 1.56 (d, 3H, JZ7.1 Hz, H-1), 2.36–2.50 (m, 2H, H-4),
4.01 (q, 1H, JZ7.1 Hz, H-2), 4.44 (s, 2H, CH2Ph), 7.06–
7.47 (m, 10H, Ph).
5.2.3. N-Benzyl-2-(phenylselanyl)butan-1-amine 6c.
Yield: 72%. 1H NMR d: 1.03 (t, 3H, JZ7.3 Hz, H-4),
1.60–1.74 (m, 2H, H-3), 1.80 (sl, 1H, NH), 2.65–2.82 (m,
2H, H-1), 3.17–3.25 (m, 1H, H-2), 3.75 (d, 1H, JZ13.6 Hz,
CH2Ph), 3.82 (d, 1H, JZ13.6 Hz, CH2Ph), 7.17–7.32 (m,
8H, Ph), 7.47–7.51 (m, 2H, Ph). 13C NMR d: 12.6 (C-4),
27.0 (C-3), 49.4 (C-2), 52.8 (C-1), 53.8 (CH2Ph), 126.9,
127.3, 127.7, 128.2, 128.5, 129.0, 135.4, 140.4 (Ph). Anal.
Calcd for C17H21NSe: C, 64.14; H, 6.65; N, 4.40. Found: C,
64.35; H, 6.72; N, 4.29.
5.1.14. Phenyl-N-(1-phenyl-2-(phenylselanyl)propyli-
dene) methanamine 2n.4a 1H NMR d: 1.54 (d, 3H, JZ
7.2 Hz, H-3), 4.22–4.38 (m, 1H, H-2), 4.29 (s, 2H, CH2Ph),
7.11–7.45 (m, 15H, Ph).
5.1.15. Phenyl-N-(2-(phenylselanyl)cyclohexylidene)
methanamine 2o.4a
1H NMR d: 1.40–2.40 (m, 8H, Cy), 4.07–4.20 (m, 1H, H-2),

452
C. Miniejew et al. / Tetrahedron 61 (2005) 447–456
5.2.4. N-Benzyl-3-methyl-2-(phenylselanyl)butan-1-
5.2.10. N-Benzyl-1-(phenylselanyl)propan-2-amine 6j.4a
Yield: 50%. 1H NMR d: 1.18 (d, 3H, JZ6.1 Hz, CH3), 1.80
(sl, 1H, NH), 2.85–3.09 (m, 3H, H-1, H-2), 3.70 (d, 1H, JZ
13.1 Hz, CH2Ph), 3.80 (d, 1H, JZ13.1 Hz, CH2Ph), 7.20–
7.35 (m, 8H, Ph), 7.45–7.49(m, 2H, Ph). 13C NMR d: 20.8
(C-3), 36.3 (C-1), 51.3 (CH2Ph), 51.7 (C-2), 127.0, 127.3,
128.2, 128.5, 129.2, 130.4, 133.0, 140.4 (Ph). Anal. Calcd
for C16H19NSe: C, 63.15; H, 6.30; N, 4.60. Found: C, 63.47;
H, 6.39; N, 4.27.
1
amine 6d.4a Yield: 69%. H NMR d: 1.01 (d, 3H, JZ
6.7 Hz, H-4), 1.05 (d, 3H, JZ6.7 Hz, H-4), 2.00–2.06 (m,
1H, H-3), 2.20 (sl, 1H, NH), 2.81 (dd, 1H, JZ8.4, 12.5 Hz,
H-1), 2.91 (dd, 1H, JZ5.1, 12.5 Hz, H-1), 3.24–3.29 (m,
1H, H-2), 3.70 (d, 1H, JZ13.4 Hz, CH2Ph), 3.75 (d, 1H, JZ
13.4 Hz, CH2Ph), 7.17–7.33 (m, 8H, Ph), 7.52–7.59 (m, 2H,
Ph). 13C NMR d: 20.1 (C-4), 21.0 (C-4), 31.2 (C-3), 51.7
(C-1), 53.6 (CH2Ph), 56.7 (C-2), 126.8, 127.1, 127.4, 128.0,
128.3, 128.9, 134.3, 140.2 (Ph). Anal. Calcd for C18H23NSe:
C, 65.05; H, 6.98; N, 4.21. Found: C, 64.86; H, 6.71, N,
4.49.
5.2.11. N-Benzyl-3,3-dimethyl-1-(phenylselanyl)butan-2-
amine 6k.4a Yield: 71%. 1H NMR d: 1.06 (s, 9H, C(CH3)3),
1.37 (sl, 1H, NH), 2.59 (dd, 1H, JZ9.0, 3.4 Hz, H-1), 3.00
(dd, 1H, JZ12.1, 9.0 Hz, H-2), 3.39 (dd, 1H, JZ12.1,
3.4 Hz, H-2), 3.85 (d, JZ12.4 Hz, CH2Ph), 4.06 (d, JZ
12.4 Hz, CH2Ph), 7.28–7.45 (m, 8H, Ph), 7.58–7.62 (m, 2H,
Ph). 13C NMR d: 27.1 (C-4), 32.3 (C-1), 36.4 (C-3), 55.4
(CH2Ph), 66.6 (C-2), 126.8, 127.3, 128.0, 128.4, 129.1,
130.0, 133.6, 141.1 (Ph). Anal. Calcd for C19H25NSe: C,
65.88; H, 7.28; N, 4.04. Found: C, 66.10; H, 7.31; N, 4.29.
5.2.5. N-Benzyl-2-(phenylselanyl)hexan-1-amine 6e.
Yield: 65%. 1H NMR d: 0.87 (t, 3H, JZ7.2 Hz, H-6),
1.22–1.55 (m, 4H, H5, H-4), 1.56–1.60 (m, 2H, H-3), 1.80
(sl, 1H, NH), 2.67 (dd, 1H, JZ7.9, 12.3 Hz, H-1), 2.77 (dd,
1H, JZ4.8, 12.3 Hz, H-1), 3.21–3.31(m, 1H, H-2), 3.74 (d,
1H, JZ13.4 Hz, CH2Ph), 3.81 (d, 1H, JZ13.4 Hz, CH2Ph),
7.21–7.34 (m, 8H, Ph), 7.47–7.51 (m, eH, Ph). 13C NMR d:
´
14.1 (C-6), 22.6 (C-5), 30.1 (C-4), 33.6 (C-3), 47.5 (C-2),
53.0 (C-1), 53.7 (CH2Ph), 127.0, 127.7, 128.2, 128.3, 128.5,
129.0, 135.4, 140.4 (Ph). Anal. Calcd for C19H25NSe: C,
65.88; H, 7.27; N, 4.04. Found: C, 66.14; H, 6.95; N, 4.27.
5.2.12. N-Benzyl-1-phenyl-2-(phenylselanyl)ethan-1-
1
amine 6l. Yield: 68%. 77Se NMR d: 268.5. H NMR d:
2.25(sl, 1H, NH), 3.06 (dd, 1H, JZ9.7, 12.3 Hz, H-2), 3.22
(dd, 1H, JZ4.3, 12.3 Hz, H-2), 3.49 (d, 1H, JZ13.4 Hz,
CH2Ph), 3.70 (d, 1H, JZ13.4 Hz, CH2Ph), 3.75 (dd, 1H,
JZ4.3, 9.7 Hz, H-1), 7.20–7.32 (m, 13H, Ph), 7.40–7.44 (m,
2H, Ph). 13C NMR d: 37.0 (C-2), 51.6 (CH2Ph), 61.1 (C-1),
127.0, 127.2, 127.3, 127.7, 128.3, 128.5, 128.8, 129.2,
129.8, 133.2, 140.4, 143.0 (Ph). Anal. Calcd for C21H21NSe:
C, 68.84; H, 5.78; N, 3.82. Found: C, 68.86; H, 5.96; N,
4.19.
5.2.6. N-Benzyl-3-phenyl-2-(phenylselanyl)propan-1-
amine 6f. Yield: 67%. 1H NMR d: 2.67–2.87 (m, 2H,
H-1), 2.94–3.14 (m, 2H, H-3), 3.50–3.65 (m, 1H, H-2), 3.71
(d, 1H, JZ13.5 Hz, CH2Ph), 3.81 (d, 1H, JZ13.5 Hz,
CH2Ph), 7.15–7.40 (m, 13H, Ph), 7.47–7.53 (m, 2H, Ph).
13C NMR d: 40.3 (C-3), 47.5 (C-2), 51.7, 53.5 (C-1,
CH2Ph), 126.9, 127.7, 128.2, 128.4, 129.0, 129.1, 135.3,
139.6 (Ph). Anal. Calcd for C22H23NSe: C, 69.46; H, 6.09;
N, 3.68. Found: C, 69.30; H, 6.12; N, 3.55.
5.2.13. N-Benzyl-2-(phenylselanyl)pentan-3-amine 6m.4a
Yield: 57%, syn/anti: 80/20. Diastereomer syn; 1H NMR d:
0.89 (t, 3H, JZ7.4 Hz, H-5), 1.41 (d, 3H, JZ7.1 Hz, H-1),
1.42–1.51 (m, 1H, H-4), 1.66–1.77 (m, 1H, H-4), 2.00 (sl,
1H, NH), 2.57 (dt, 1H, JZ4.9, 6.6 Hz, H-3), 3.46 (qd, 1H,
JZ4.9, 7.1 Hz, H-2), 3.74 (d, 1H, JZ13.3 Hz, CH2Ph), 3.79
(d, 1H, JZ13.3 Hz, CH2Ph), 7.15–7.32 (m, 8H, Ph), 7.50–
7.54 (m, 2H, Ph). 13C NMR d: 10.4 (C-5), 18.8 (C-1), 23.9
(C-4), 44.7 (C-2), 51.9 (CH2Ph), 62.7 (C-3), 127.0, 127.4
128.3, 128.5, 129.0, 129.4, 134.9, 140.2 (Ph). Diastereomer
anti; 1H NMR d: 0.88 (t, 3H, JZ7.4 Hz, H-5), 1.39 (d, 3H,
JZ7.1 Hz, H-1), 1.50–1.60 (m, 1H, H-4), 1.66–1.76 (m, 1H,
H-4), 2.00 (sl, 1H, NH), 2.52–2.59 (m, 1H, H-3), 3.60–3.65
(m, 1H, H-2), 3.88 (m, 2H, CH2Ph), 7.15–7.32 (m, 8H, Ph),
7.48–7.52 (m, 2H, Ph). 13C NMR d: 11.2 (C-5), 17.6 (C-1),
24.7 (C-4), 45.3 (C-2), 51.9 (CH2Ph), 62.7 (C-3), 127.8,
128.8, 129.0, 129.9, 130.2, 134.9, 135.3, 139.8 (Ph). Anal.
Calcd for C18H23NSe: C, 65.05; H, 6.98; N, 4.21. Found: C,
65.36; H, 6.81; N, 4.59.
5.2.7. N-Benzyl-2-methyl-2-(phenylselanyl)propan-1-
1
amine 6g.4a Yield: 64%. H NMR d: 1.40 (s, 6H, H-3),
1.84 (sl, 1H, NH), 2.50 (s, 2H, H-1), 3.86 (s, 2H, CH2Ph),
7.25–7.40 (m, 8H, Ph), 7.47–7.53 (m, 2H, Ph). 13C NMR d:
28.4 (C-3), 48.4 (C-2), 54.0 (CH2Ph), 59.2 (C-1), 126.8,
127.0, 127.6, 128.1, 128.3, 128.9, 134.2, 141.1 (Ph). Anal.
Calcd for C17H21NSe: C, 64.14; H, 6.65; N, 4.40. Found: C,
64.45; H, 6.79; N, 4.19.
5.2.8. N-Benzyl-2-phenyl-2-(phenylselanyl)propan-1-
1
amine 6h. Yield: 59%. 77Se NMR d: 564.8. H NMR d:
1.50 (sl, 1H, NH), 1.84 (s, 3H, H-3), 3.00 (d, 1H, JZ
12.0 Hz, H-1), 3.25 (d, 1H, JZ12.0 Hz, H-1), 3.79 (s, 2H,
CH2Ph), 7.10–7.35 (m, 15H, Ph). 13C NMR d: 26.0 (C-3),
52.7 (C-2), 54.2 (CH2Ph), 58.7 (C-1), 126.8, 127.0, 127.4,
127.8, 128.2, 128.3, 128.5, 128.6, 128.7, 137.9, 140.5, 144.1
(Ph). Anal. Calcd for C22H23NSe: C, 69.46; H, 6.09; N,
3.68. Found: C, 69.26; H, 5.86; N, 3.98.
5.2.14. syn-N-Benzyl-1-phenyl-2-(phenylselanyl)propan-
1
1-amine 6n.4a Yield: 53%. H NMR d: 1.30 (d, 3H, JZ
5.2.9. Phenyl-N-((1-(phenylselanyl)cyclohexyl)methyl)
methanamine 6i. Yield: 51%. H NMR d: 0.90–1.90 (m,
7.1 Hz, H-3), 2.20 (sl, 1H, NH), 3.47 (d, 1H, JZ13.3 Hz,
CH2Ph), 3.61 (qd, 1H, JZ3.5, 7.1 Hz, H-2), 3.76 (d, 1H, JZ
13.3 Hz, CH2Ph), 3.83 (d, 1H, JZ3.4 Hz, H-1), 7.20–7.40
(m, 13H, Ph), 7.46–7.50 (m, 2H, Ph). 13C NMR d: 15.7
(C-3), 47.3 (C-2), 51.7 (CH2Ph), 64.3 (C-1), 127.0, 127.4,
127.7, 128.0, 128.3, 128.4, 129.2, 129.4, 129.6, 135.0,
140.5, 141.0 (Ph). Anal. Calcd for C22H23NSe: C, 69.47; H,
6.09; N, 3.68. Found: C, 69.82; H, 6.31; N, 3.49.
1
11H, Cy, NH), 2.47–2.52 (m, 2H, H-1), 3.81 (s, 2H,
CH2Ph), 7.20–7.45 (m, 8H, Ph), 7.57–7.64 (m, 2H, Ph). 13
C
NMR d: 26.1, 31.4, 35.5, 53.2, 54.0 56.1 (C-1, CH2Ph),
126.7, 128.0, 128.2, 128.5, 129.0, 131.3, 137.9, 140.4 (Ph).
Anal. Calcd for C20H25NSe: C, 67.02; H, 7.03; N, 3.91.
Found: C, 66.73; H, 6.86; N, 3.78.

C. Miniejew et al. / Tetrahedron 61 (2005) 447–456
453
5.2.15. N-Benzyl-2-(phenylselanyl)cyclohexanamine
5.3.1. N-Benzyl-3-methyl-5-(phenylselanyl)non-1-en-4-
amine 10e. Yield: 56%, two diastereomers: 70/30. Major
diastereomer; 1H NMR d: 0.86 (t, 3H, JZ7.2 Hz, H-9), 1.06
(d, 3H, JZ6.6 Hz, CH3), 1.20–1.50 (m, 4H, H-8, H-7), 1.51
(sl, 1H, NH), 1.80–1.98 (m, 2H, H-6), 2.55 (dd, 1H, JZ2.4,
7.4 Hz, H-4), 2.58–2.72 (m, 1H, H-3), 3.32 (td, 1H, JZ2.4,
7.2 Hz, H-5), 3.83 (s, 2H, CH2Ph), 5.06–5.16 (m, 2H, H-1),
5.76–5.88 (m, 1H, H-2), 7.25–7.40 (m, 8H, Ph), 7.55–7.58
(m, 2H, Ph). 13C NMR d: 14.1 (C-9), 18.8 (CH3), 22.6 (C-8),
30.6 (C-7), 35.4 (C-6), 42.9 (C-3), 53.4 (C-5), 54.7 (CH2Ph),
64.4 (C-4), 115.6 (C-1), 140.9 (C-2), 126.9, 127.0, 128.4,
128.9, 129.0, 131.7, 134.4, 142.1 (Ph). Minor diastereomer;
1H NMR d: 0.89 (t, 3H, JZ7.0 Hz, H-9), 1.06 (d, 3H, JZ
6.7 Hz, CH3), 1.19–1.99 (m, 7H, H-8, H-7, H-6, NH), 2.49–
2.61 (m, 1H, H-3), 2.71–2.76 (m, 1H, H-4), 3.43–3.52 (m,
1H, H-5), 3.81 (d, 1H, JZ12.3 Hz, CH2Ph), 3.88 (d, 1H, JZ
12.3 Hz, CH2Ph), 5.00–5.06 (m, 2H, H-1), 5.70–5.83 (m,
1H, H-2), 7.25–7.40 (m, 8H, Ph), 7.55–7.58 (m, 2H, Ph).
13C NMR d: 14.4 (C-9), 17.6 (CH3), 22.9 (C-8), 31.2 (C-7),
31.4 (C-6), 42.2 (C-3), 52.6 (C-5), 54.8 (CH2Ph), 65.7 (C-4),
114.5 (C-1), 142.9 (C-2), 127.3, 127.5, 128.6, 128.7, 129.4,
131.5, 134.5, 143.0 (Ph). Anal. Calcd for C23H31NSe: C,
68.98; H, 7.80; N, 3.50. Found: C, 68.62; H, 7.91; N, 3.36.
1
6o.4a Yield: 57%, syn/anti: 80/20. Diastereomer syn; H
NMR d: 1.20–2.20 (m, 9H), 2.76 (m, 1H, H-1), 3.74 (s, 2H,
CH2Ph), 3.81 (m, 1H, H-2), 7.20–7.40 (m, 8H, Ph) 7.45–
7.49 (m, 2H, Ph). 13C NMR d: 23.5, 23.8, 30.3, 31.2, 50.7
(CH2Ph), 52.2 (C-2), 57.5 (C-1), 126.9, 127.0, 128.4, 129.1,
1
129.6, 129.8, 134.9, 141.0 Diastereomer anti; H NMR d:
1.20–2.20 (m, 9H), 2.45 (m, 1H, H-1), 3.08 (m, 1H, H-2),
3.71 (d, 1H, JZ13.1 Hz, CH2Ph), 3.93 (d, 1H, JZ13.1 Hz,
CH2Ph), 7.15–7.35 (m, 8H, Ph), 7.40–7.43 (m, 2H, Ph). 13
C
NMR d: 24.7, 27.4, 32.5, 34.4, 50.9 (C-2), 51.0 (CH2Ph),
59.6 (C-1), 127.0, 128.3, 128.5, 129.1, 129.6, 129.8, 135.1,
140.5 (Ph). Anal. Calcd for C19H23NSe: C, 66.27; H, 6.73;
N, 4.07. Found: C, 66.17; H, 6.67; N, 4.12.
5.2.16. N-Allyl-2-(phenylselanyl)butan-1-amine 7c.
1
Yield: 64%. bp0.05: 93 8C. H NMR d: 1.03 (t, 3H, JZ
7.2 Hz, H-4), 1.58–1.81 (m, 2H, H-3), 2.10 (sl, 1H, NH),
2.63–2.83 (m, 2H, H-1), 3.14–3.28 (m, 3H, H-2,
CH2CH]CH2), 5.02–5.20 (m, 2H, CH2CH]CH2), 5.77–
5.97 (m, 1H, CH2CH]CH2), 7.18–7.28 (m, 3H, Ph), 7.50–
7.63 (m, 2H, Ph). 13C NMR d 12.4 (C-4), 26.8 (C-3), 49.2
(C-2), 52.0 (CH2CH]CH2), 52.7 (C-1), 115.9
(CH2CH]H2), 127.5, 127.6, 128.9, 129.1, 131.4, 135.1,
136.7 (Ph, CH2CH]CH2). Anal. Calcd for C13H19NSe: C,
58.20; H, 7.14; N, 5.22. Found: C, 58.02; H, 7.30; N, 4.94.
5.3.2. N-Benzyl-6-methyl-5-(phenylselanyl)hept-1-en-4-
amine 11d. Yield: 78%, syn/anti: 55/45. Diastereomer
syn; 1H NMR d: 1.02 (d, 3H, JZ6.6 Hz, H-7), 1.06 (d, 3H,
JZ6.6 Hz, H-7), 1.68 (sl, 1H, NH), 2.16 (m, 1H, H-6), 2.48
(m, 2H, H-3), 2.88 (m, 1H, H-4), 3.10–3.14 (m, 1H, H-5),
3.74 (d, 1H, JZ13.1 Hz, CH2Ph), 3.89 (d, 1H, JZ13.1 Hz,
CH2Ph), 4.93–5.05 (m, 2H, H-1), 5.69–5.79 (m, 1H, H-2),
7.22–7.34 (m, 8H, Ph), 7.55–7.58 (m, 2H, Ph). 13C NMR d:
21.5 (C-7), 22.1 (C-7), 31.5 (C-6), 37.3 (C-3), 52.0 (CH2Ph),
59.0 (C-4), 62.4 (C-5), 117.4 (C-1), 135.9 (C-2), 126.8,
127.0, 128.3, 128.4, 129.0, 132.1, 133.8, 140.7 (Ph).
5.2.17. N-Cyclohexyl-2-(phenylselanyl)butan-1-amine
1
8c. Yield: 57%. 77Se NMR d: 332.9. H NMR d: 1.07 (t,
3H, JZ7.2 Hz, H-4), 1.10–1.31 (m, 6H, Cy), 1.57–1.85 (m,
7H, Cy, H-3, NH), 2.38 (m, 1H, Cy), 2.69 (dd, 1H, JZ8.9,
12.5 Hz, H-1), 2.85 (dd, 1H, JZ4.8, 12.5 Hz, H-1), 3.16–
3.25 (m, 1H, H-2), 7.25–7.40 (m, 3H, Ph), 7.55–7.60 (m,
2H, Ph). 13C NMR d: 12.5 (C-4), 25.1, 26.2, 27.0 (Cy), 33.8
(C-3), 49.7 (C-2), 50.6 (C-1), 56.6 (Cy), 127.6, 129.0, 128.9,
135.4 (Ph). Anal. Calcd for C16H25NSe: C, 61.92; H, 8.12;
N, 4.51. Found: C, 61.58; H, 7.87; N, 4.71.
1
Diastereomer anti; H NMR d: 1.07 (d, 3H, JZ6.6 Hz,
H-7), 1.15 (d, 3H, JZ6.6 Hz, H-7), 1.66 (sl, 1H, NH), 2.12–
2.20 (m, 1H, H-6), 2.26–2.34 (m, 1H, H-3), 2.44–2.54 (m,
1H, H-3), 2.85–2.95 (m, 1H, H-4), 3.23–3.27 (m, 1H, H-5),
3.68 (s, 2H, CH2Ph), 4.99–5.10 (m, 2H, H-1), 5.70–5.90 (m,
1H, H-2), 7.22–7.35 (m, 8H, Ph), 7.55–7.60 (m, 2H, Ph).
13C NMR d: 21.5 (C-7), 22.1 (C-7), 31.0 (C-6), 36.8 (C-3),
51.6 (CH2Ph), 59.2 (C-4), 62.8 (C-5), 116.9 (C-1), 136.3
(C-2), 126.8, 127.0, 128.3, 128.4, 129.0, 132.1, 133.8, 140.7
(Ph). Anal. Calcd for C21H27NSe: C, 67.73; H, 7.31; N,
3.76. Found: C, 67.61; H, 7.56; N, 3.59.
5.2.18. N-tert-Butyl-2-(phenylselanyl)butan-1-amine 9c.
Yield: 56%. 1H NMR d: 1.07 (t, 3H, JZ7.4 Hz, H-4), 1.10
(s, 9H, C(CH3)3), 1.65–1.81 (m, 2H, H-3), 2.67–2.80
(dd, 1H, JZ7.9, 11.8 Hz, H-1), 2.66 (dd, 1H, JZ5.1,
11.8 Hz, H-1), 3.11–3.22 (m, 1H, H-2), 7.25–7.30 (m, 3H,
Ph), 7.55–7.60 (m, 2H, Ph). 13C NMR d: 12.5 (C-4), 27.2
(C-3), 29.3 (C(CH3)3), 46.4 (C-1), 50.1 (C-2), 50.3
(C(CH3)3), 127.6, 128.6, 129.0, 135.3 (Ph). Anal. Calcd
for C14H23NSe: C, 59.14; H, 8.15; N, 4.93. Found: C, 58.86;
H, 7.92; N, 4.65.
5.3.3. syn-N-Benzyl-5-(phenylselanyl)non-1-en-4-amine
11e. Yield: 69%. 1H NMR d: 0.87 (t, 3H, JZ7.2 Hz,
H-9), 1.22–1.35 (m, 3H, H-8, H-7), 1.42–1.63 (m, 3H, H-7,
H-6 NH), 1.84–1.95 (m, 1H, H-6), 2.20–2.31 (m, 1H, H-3),
2.51–2.62 (m, 1H, H-3), 2.76–2.82 (m, 1H, H-4), 3.24–3.32
(m, 1H, H-5), 3.74 (d, 1H, JZ13.4 Hz, CH2Ph), 3.80 (d, 1H,
JZ13.4 Hz, CH2Ph), 4.99–5.07 (m, 2H, H-1), 5.64–5.78
(m, 1H, H-2), 7.22–7.35 (m, 8H, Ph), 7.55–7.60 (m, 2H, Ph).
13C NMR d: 14.1 (C-9), 22.6 (C-8), 30.7 (C-7), 31.9 (C-6),
36.5 (C-3), 52.0 (CH2Ph), 52.2 (C-5), 59.8 (C-4), 117.5
(C-1), 136.2 (C-2), 127.0, 127.2, 128.3, 128.4, 129.0, 130.8,
134.4, 140.8 (Ph). Anal. Calcd for C22H29NSe: C, 68.38; H,
7.56; N, 3.62. Found: C, 68.52; H, 7.91; N, 3.86.
5.3. Preparation of b-phenylselanyl amines 10e and 11
A solution of alkylmagnesium chloride 2M in THF (1.1 ml,
2.2 mmol) was slowly added to a-phenylselanyl imines 2
(2 mmol) in THF (30 ml), at K40 8C, under argon. The
whole was stirred for 30 min at K40 8C and allowed to
reach 0 8C in 2 h. A saturated aqueous solution of
ammonium chloride (5 ml) was added, followed by a
mixture of water/ether: 1/1 (40 ml). After separation, the
aqueous phase was washed with ether (2!50 ml). The
combined organic phases were dried over MgSO4 and
concentrated. The crude product was purified by column
chromatography on silica gel (cyclohexane/Et2O: 95/5).
5.3.4. N-Benzyl-2-methyl-2-(phenylselanyl)hex-5-en-3-
amine 11g. Yield: 74%. H NMR d: 1.38 (s, 3H, H-1),
1

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C. Miniejew et al. / Tetrahedron 61 (2005) 447–456
1.44 (s, 3H, H-1), 1.55 (sl, 1H, NH), 2.14–2.25 (m, 1H,
H-4), 2.63–2.77 (m, 2H, H-4, H-3), 3.78 (d, 1H, JZ12.6 Hz,
CH2Ph), 3.92 (d, 1H, JZ12.6 Hz, CH2Ph), 5.06–5,16 (m,
2H, H-6), 5.83–5.98 (m, 1H, H-5), 7.25–7.40 (m, 8H, Ph),
7.62–7.65 (m, 2H, Ph). 13C NMR d: 27.0 (C-1), 27.7 (C-1),
37,0 (C-4), 54.6 (CH2Ph), 65.6 (C-3), 77.36 (C-2), 116.8
(C-6), 137.1 (C-5), 127.0, 127.4, 128.3, 128.4, 128.5, 128.7,
138.5, 140.8 (Ph). Anal. Calcd for C20H25NSe: C, 67.03; H,
7.03; N, 3.91. Found: C, 67.31; H, 7.27; N, 3.79.
(2 mmol) in refluxing THF (30 ml), under argon. The whole
was stirred for 2 h under reflux. A saturated aqueous
solution of ammonium chloride (5 ml) was added, followed
by a mixture of water/ether: 1/1 (40 ml). After separation,
the aqueous phase was washed with ether (2!50 ml). The
combined organic phases were dried over MgSO4 and
concentrated. The crude product was purified by column
chromatography on silica gel (cyclohexane/Et2O: 80/20).
5.4.1. 2-Allyl-1-benzyl-3-isopropylaziridine 12d. Yield:
73%, cis/trans: 55/45. Diastereomer cis; 1H NMR d: 0.84 (d,
3H, JZ6.1 Hz, CH(CH3)2), 0.90 (d, 3H, JZ6.7 Hz,
CH(CH3)2), 1.23 (dd, 1H, JZ6.5, 9.6 Hz H-3), 1.28–1.38
(m, 1H, CH(CH3)2), 1.55–1.63 (m, 1H, H-2), 2.13–2.25
(m, 2H, CH2CH]CH2), 3.37 (d, 1H, JZ12.6 Hz, CH2Ph),
3.49 (d, 1H, JZ12.6 Hz, CH2Ph), 4.97–5.11 (m, 2H,
CH2CH]CH2), 5.70–5.87 (m, 1H, CH2CH]CH2), 7.26–
7.36 (m, 5H, Ph). 13C NMR d: 20.4 (CH(CH3)2), 21.4
(CH(CH3)2), 27.7 (CH(CH3)2), 32.9 (CH2CH]CH2), 44.3
(C-2), 51.5 (C-3), 65.8 (CH2Ph), 115.8 (CH2CH]H2),
139.3 (CH2CH]CH2), 126.9, 127.2, 128.3, 139.7 (Ph). MS
m/z: 215 (MC, 2), 172 (27), 124 (4), 91 (39), 55 (100). Anal.
Calcd for C15H21N: C, 83.66; H, 9.83; N, 6.50. Found: C,
5.3.5. syn-N-Benzyl-2-phenyl-2-(phenylselanyl)hex-5-en-
3-amine 11h. Yield: 47%. H NMR d: 1.57 (sl, 1H, NH),
1
1.86 (s, 3H, H-1), 1.96–2.06 (m, 1H, H-4), 2.18–2.25 (m,
1H, H-4), 3.62 (dd, 1H, JZ3.2, 8.3 Hz, H-3), 4.06 (d, 1H,
JZ12.3 Hz, CH2Ph), 4.13 (d, 1H, JZ12.3 Hz, CH2Ph),
4.93–4.99 (m, 2H, H-6), 5.70–5.84 (m, 1H, H-5), 6.99–7.52
(m, 15H, Ph). 13C NMR d: 21.5 (C-1), 37.7 (C-4), 55.0
(CH2Ph), 61.4 (C-2), 65.7 (C-3), 116.7 (C-6), 136.7 (C-5),
126.3, 127.1, 127.6, 127.8, 128.0, 128.3, 128.5, 128.7,
129.4, 137.6, 140.7, 144.1 (Ph). Anal. Calcd for C25H27NSe:
C, 71.41; H, 6.47; N, 3.33. Found: C, 71.02; H, 6.19; N,
3.03.
1
5.3.6. N-Benzyl-2-methyl-1-(phenylselanyl)pent-4-en-2-
amine 11j. Yield: 58%. H NMR d: 1.26 (s, 3H, CH3),
83.40; H, 9.82; N, 6.61. Diastereomer trans; H NMR d:
1
0.74 (d, 3H, JZ6.4 Hz, CH(CH3)2), 0.88 (d, 3H, JZ6.7 Hz,
CH(CH3)2), 1.14 (dd, 1H, JZ2.3, 9.2 Hz H-3), 1.19–1.27
(m, 1H, CH(CH3)2), 1.87–1.97 (m, 1H, H-2), 2.19–2.36 (m,
1H, CH2CH]CH2), 2.42–2.54 (m, 1H, CH2CH]CH2),
3.39 (d, 1H, JZ13.3 Hz, CH2Ph), 3.86 (d, 1H, JZ13.3 Hz,
CH2Ph), 4.97–5.20 (m, 2H, CH2CH]CH2), 5.82–5.97 (m,
1H, CH2CH]CH2), 7.19–7.37 (m, 5H, Ph). 13C NMR d:
19.9 (CH(CH3)2), 20.6 (CH(CH3)2), 31.0 (CH2CH]CH2),
31.8 (CH(CH3)2), 42.0 (C-2), 52.8 (C-3), 56.5 (CH2Ph),
116.3 (CH2CH]CH2), 136.1 (CH2CH]CH2), 126.9,
128.2, 128.4, 140.2 (Ph). MS m/z: 215 (MC, 2), 172 (27),
124 (4), 91 (38), 55 (100).
1.57 (sl, 1H, NH), 2.30–2.51 (m, 2H, H-3), 3.16 (d, 1H, JZ
11.8 Hz, H-1), 3.26 (d, 1H, JZ11.8 Hz, H-1), 3.69 (s, 2H,
CH2Ph), 5.11–5.18 (m, 2H, H-5), 5.81–5.93 (m, 1H, H-4),
7.25–7.38 (m, 8H, Ph), 7.55–7.59 (m, 2H, Ph). 13C NMR d:
25.0 (CH3), 40.2 (C-1), 43.7 (C-3), 46.5 (CH2Ph), 55.9
(C-2), 118.6 (C-5), 134.2 (C-4), 126.8, 127.0, 128.2, 128.4,
129.2, 131.5, 132.9, 140.9 (Ph). Anal. Calcd for C20H25NSe:
C, 67.03; H, 7.03; N, 3.91. Found: C, 66.96; H, 6.75; N,
4.02.
5.3.7. N-Benzyl-2-phenyl-1-(phenylselanyl)pent-4-en-2-
amine 11l. Yield: 65%. H NMR d: 1.88 (sl, 1H, NH),
1
2.65–2.80 (m, 2H, H-3), 3.45 (d, 1H, JZ12.0 Hz, CH2Ph),
3.55 (d, 1H, JZ12.0 Hz, CH2Ph), 3.62 (s, 2H, H-1), 4.99–
5.07 (m, 2H, H-5), 5.43–5.58 (m, 1H, H-4), 7.20–7.60 (m,
15H, Ph). 13C NMR d: 38.9 (C-1), 44.2 (C-3), 46.7 (CH2Ph),
61.5 (C-2), 118.8 (C-5), 133.5 (C-4), 126.8, 126.9, 127.0,
128.3, 128.4, 128.5, 129.1, 131.2, 133.3, 140.7, 144.0 (Ph).
Anal. Calcd for C24H25NSe: C, 70.92; H, 6.20; N, 3.44.
Found: C, 70.55; H, 6.15; N, 3.22.
5.4.2. cis-2-Allyl-1-benzyl-3-butylaziridine 12e. Yield:
53%. 1H NMR d: 0.85 (t, 3H, JZ6.6 Hz, CH2CH2CH2CH3),
1.22–1.43 (m, 6H, CH2CH2CH2CH3), 1.46–1.58 (m, 2H,
H-2, H-3), 2.07–2.18 (m, 1H, CH2CH]CH2), 2.19–2.29
(m, 1H, CH2CH]CH2), 3.44 (d, 1H, JZ13.3 Hz, CH2Ph),
3.50 (d, 1H, JZ13.3 Hz, CH2Ph), 4.96–5.10 (m, 2H,
CH2CH]CH2), 5.71–5.83 (m, 1H, CH2CH]CH2), 7.22–
7.35 (m, 5H, Ph). 13C NMR d: 14.1 (CH2CH2CH2CH3),
22.7 (CH2CH2CH2CH3), 27.9 (CH2CH2CH2CH3), 30.2
(CH2CH2CH2CH3), 32.8 (CH2CH]CH2), 43.6 (C-2),
44.2 (C-3), 65.3 (CH2Ph), 115.7 (CH2CH]H2), 136.2
(CH2CH]CH2), 127.0, 128.2, 128.4, 139.4 (Ph). MS m/z:
229 (MC, 1), 186 (9), 172 (20), 91 (65), 69 (72), 55 (80), 44
(90), 41 (100). Anal. Calcd for C16H23N: C, 83.79; H, 10.11;
N, 6.11. Found: C, 83.62; H, 10.33; N, 6.05.
5.3.8. syn-N-Benzyl-3-phenyl-2-(phenylselanyl)hex-5-en-
3-amine 11n. Yield: 64%. 77Se NMR d: 364.0. 1H NMR d:
1.31 (d, 3H, JZ6.9 Hz, H-1), 2.33 (sl, 1H, NH), 2.88 (dd,
1H, JZ5.3, 14.8 Hz, H-4), 3.08 (dd, 1H, JZ8.3, 14.8 Hz,
H-4), 3.65 (d, 1H, JZ12.5 Hz, CH2Ph), 3.74 (q, 1H, JZ
6.9 Hz, H-2), 3.82 (d, 1H, JZ12.5 Hz, CH2Ph), 5.15–5.22
(m, 2H, H-6), 5.90–5.98 (m, 1H, H-5), 7.20–7.60 (m, 15H,
Ph). 13C NMR d: 19.0 (C-1), 38.2 (C-4), 46.8 (CH2Ph), 51.6
(C-2), 64.1 (C-3), 118.5 (C-6), 134.0 (C-5), 126.9, 127.1,
127.2, 127.8, 128.0, 128.2, 128,5, 129.0, 130.8, 134.7,
140.9, 141,5 (Ph). Anal. Calcd for C25H27NSe: C, 71.41; H,
6.47; N, 3.33. Found: C, 71.12; H, 6.39; N, 3.15.
5.4.3. 3-Allyl-1-benzyl-2,2-dimethylaziridine 12g. Yield:
57%. H NMR d: 1.20 (s, 3H, CH3), 1.24 (s, 3H, CH3),
1
1.39–1.43 (m, 1H, H-3), 2.06–2.17 (m, 1H, CH2CH]CH2),
2.27–2.37 (m, 1H, CH2CH]CH2), 3.67 (s, 2H, CH2Ph),
4.95–5.08 (m, 2H, CH2CH]CH2), 5.73–5.83 (m, 1H,
CH2CH]CH2), 7.18–7.36 (m, 5H, Ph). 13C NMR d: 18.6
(CH3), 22.1 (CH3), 34.1 (CH2CH]CH2), 40.0 (C-2),
49.9 (C-3), 56.9 (CH2Ph), 115.5 (CH2CH]H2), 136.3
(CH2CH]CH2), 126.5, 127.6, 128.3, 140.6 (Ph). MS m/z:
201 (MC, 12), 186 (34), 160 (16), 110 (24), 91 (68), 55 (75).
5.4. Preparation of allylaziridines 12
A solution of allylmagnesium chloride 2M in THF (1.1 ml,
2.2 mmol) was slowly added to a-phenylselanyl imine 2

C. Miniejew et al. / Tetrahedron 61 (2005) 447–456
455
Anal. Calcd for C14H19N: C, 83.53; H, 9.51; N, 6.96. Found:
C, 83.34; H, 9.61; N, 7.05.
5.5. Cyclisation of 11j
To the b-phenylselanyl amine 11j (1 mmol) in acetonitrile
(10 ml) was added NBS (195 mg, 1.1 mmol) at room
temperature. After 5 min of stirring, the mixture became
red-brown and sodium bicarbonate (212 mg, 2 mmol) was
introduced. The mixture turned rapidly yellow. Water
(10 ml) was added and the aqueous phase was extracted
with dichloromethane (2!10 ml). The combined organic
phases were dried over MgSO4 and concentrated. The crude
product was purified by column chromatography on silica
gel (cyclohexane/Et2O: 80/20) to afford the aziridine 12j.
5.4.4. trans-3-Allyl-1-benzyl-2-methyl-2-phenylaziridine
12h. Yield: 41%. 1H NMR d: 1.54 (s, 3H, CH3), 2.04–2.09
(m, 1H, H-3), 2.22–2.34 (m, 1H, CH2CH]CH2), 2.39–2.51
(m, 1H, CH2CH]CH2), 2.78 (d, 1H, JZ14.1 Hz, CH2Ph),
3.54 (d, 1H, JZ14.1 Hz, CH2Ph), 5.01–5.18 (m, 2H,
CH2CH]CH2), 5.75–5.86 (m, 1H, CH2CH]CH2), 7.22–
7.37 (m, 10H, Ph). 13C NMR d: 22.8 (CH3), 33.9
(CH2CH]CH2), 47.9 (C-3), 48.7 (C-2), 59.0 (CH2Ph),
116.2 (CH2CH]H2), 135.9 (CH2CH]CH2), 126.7, 127.5,
128.0, 128.2, 128.3, 129.8, 140.1, 140.6 (Ph). Anal. Calcd
for C19H21N: C, 86.65; H, 8.04; N, 5.32. Found: C, 86.40; H,
8.17; N, 5.42.
5.5.1. 2-Allyl-1-benzyl-2-methylaziridine 12j. Yield:
72%. H NMR d: 1.24 (s, 1H, CH3), 1.26 (s, 1H, H-3),
1
1.87 (s, 1H, H-3), 2.04–2.30 (m, 1H, CH2CH]CH2), 3.65
(s, 2H, CH2Ph), 5.02–5.13 (m, 2H, CH2CH]CH2), 5.74–
5.88 (m, 1H, CH2CH]CH2), 7.20–7.39 (m, 5H, Ph).
13C NMR d: 14.9 (CH3), 39.9 (C-3), 45.0 (C-2), 45.2
(CH2CH]CH2), 57.1 (CH2Ph), 117.0 (CH2CH]H2),
135.4 (CH2CH]CH2), 126.8, 127.7, 128.5, 140.5 (Ph).
MS m/z: 187 (MC, 19), 146 (21), 96 (32), 91 (100), 55 (93).
Anal. Calcd for C13H17N: C, 83.37; H, 9.15; N, 7.48. Found:
C, 83.07; H, 8.94; N, 7.28.
5.4.5. 2-Allyl-1-benzyl-2-phenylaziridine 12l. Yield:
61%. H NMR d: 1.88 (s, 1H, H-3), 2.12 (s, 1H, H-3),
1
2.27 (dd, 1H, JZ7.2, 14.1 Hz, CH2CH]CH2), 2.85 (d,
1H, JZ14.1 Hz, CH2Ph), 2.90 (dd, 1H, JZ7.2, 14.1 Hz,
CH2CH]CH2), 3.45 (d, 1H, JZ14.1 Hz, CH2Ph), 4.91–4.99
(m, 2H, CH2CH]CH2), 5.62–5.76 (m, 1H, CH2CH]CH2),
7.19–7.37 (m, 10H, Ph). 13C NMR d: 38.0 (C-3), 45.2
(CH2CH]CH2), 48.9 (C-2), 58.7 (CH2Ph), 117.1
(CH2CH]H2), 134.6 (CH2CH]CH2), 126.8, 127.0,
127.2, 127.4, 127.7, 128.2, 137.5, 140.1 (Ph). MS m/z:
249 (MC, 24), 208 (10), 172 (5), 158 (30), 91 (100), 77 (20),
55 (75). Anal. Calcd for C18H19N: C, 86.70; H, 7.68; N,
5.62. Found: C, 86.32; H, 7.56; N, 5.32.
Acknowledgements
The authors want to thank the region Haute-Normandie for
their financial support (PhD fellowship to C. M.). A special
thank to Claudette Martin who prepared a lot of the starting
materials.
5.4.6. cis-2-Allyl-1-benzyl-2-ethyl-3-methylaziridine
12m. Yield: 57%. 1H NMR d: 0.98 (t, 3H, JZ7.2 Hz,
CH2CH3), 1.20 (d, JZ5.6 Hz, 3H, CH3), 1.47 (q, 1H, JZ
5.6 Hz, H-3), 1.52–1.63 (m, 2H, CH2CH3), 2.16 (dd, 1H,
JZ7.3, 14.6 Hz, CH2CH]CH2), 2.28 (dd, 1H, JZ7.3,
14.6 Hz, CH2CH]CH2), 3.59 (d, 1H, JZ14.1 Hz, CH2Ph),
3.83 (d, 1H, JZ14.1 Hz, CH2Ph), 5.02–5,15 (m, 2H,
CH2CH]CH2), 5.70–5.85 (m, 1H, CH2CH]CH2), 7.22–
7.39 (m, 5H, Ph). 13C NMR d: 10.9 (CH2CH3), 14.6 (CH3),
22.4 (CH2CH3), 36.8 (CH2CH]CH2), 45.3 (C-3), 47.0 (C-2),
56.5 (CH2Ph), 116.7 (CH2CH]H2), 135.8 (CH2CH]CH2),
126.7, 127.9, 128.5, 140.7 (Ph). MS m/z: 215 (MC, 1), 200
(25), 186 (13), 124 (15), 91 (72), 69 (85), 56 (40), 41 (100).
Anal. Calcd for C15H21N: C, 83.67; H, 9.83; N, 6.50. Found:
C, 83.77; H, 9.72; N, 6.51.
References and notes
1. Nicolaou, K. C.; Petasis, N. A. Selenium in Natural Products
Synthesis; CIS: Philadelphia, 1984. Paulmier, C. Selenium
Reagents and Intermediates in Organic Synthesis; Pergamon:
Oxford, 1986. Patai, S.; Rappoport, Z. The Chemistry of
Organic Selenium and Tellurium Compounds; Wiley: New
York, 1986. Liotta, D. Organoselenium Chemistry; Wiley:
New York, 1987. Krief, A.; Hevesi, L. Organoselenium
Chemistry; Springer: Berlin, 1988. Back, T. G. Organosele-
nium Chemistry: A Practical Approach; Oxford University
Press: Oxford, 1999. Wirth, T. Organoselenium Chemistry:
Modern Developments in Organic Synthesis; Springer: Berlin,
2000. Mugesh, G.; du Mont, W.-W. Chem. Rev. 2001, 101,
2125.
5.4.7. trans-2-Allyl-1-benzyl-3-methyl-2-phenylaziridine
12n. Yield: 41%. 1H NMR d: 1.38 (d, JZ5.6 Hz, 3H, CH3),
2.12 (q, 1H, JZ5.6 Hz, H-3), 2.38 (dd, 1H, JZ6.9, 14.6 Hz,
CH2CH]CH2), 2.79 (d, 1H, JZ14.3 Hz, CH2Ph), 2.91 (dd,
1H, JZ6.9, 14.6 Hz, CH2CH]CH2), 3.56 (d, 1H, JZ
14.3 Hz, CH2Ph), 4.87–4.93 (m, 2H, CH2CH]CH2), 5.52–
5.66 (m, 1H, CH2CH]CH2), 7.17–7.31 (m, 10H, Ph). 13C
NMR d: 14.6 (CH3), 41.1 (CH2CH]CH2), 43.9 (C-3),
51.9 (C-2), 58.9 (CH2Ph), 116.9 (CH2CH]H2), 134.7
(CH2CH]CH2), 126.6, 127.5, 127.7, 128.1, 128.3, 130.6,
138.9, 140.3 (Ph). MS m/z: 263 (MC, 31), 248 (14), 220 (2),
172 (38), 91 (69), 69 (100), 41 (59). Anal. Calcd for
C19H21N: C, 86.65; H, 8.04; N, 5.32. Found: C, 86.30; H,
8.31; N, 5.37.
2. (a) Houllemare, D.; Ponthieux, S.; Outurquin, F.; Paulmier, C.
Synthesis 1997, 10. (b) Paulmier, C.; Lerouge, P. Tetrahedron
Lett. 1982, 23, 1557. Lerouge, P.; Paulmier, C. Tetrahedron
Lett. 1984, 25, 1983.
3. Ponthieux, S.; Outurquin, F.; Paulmier, C. Tetrahedron 1995,
51, 9569. Ponthieux, S.; Outurquin, F.; Paulmier, C. Tetra-
hedron 1997, 53, 6365. Ponthieux, S.; Outurquin, F.; Paulmier,
C. Tetrahedron Lett. 1998, 39, 4017.
4. (a) Boivin, S.; Outurquin, F.; Paulmier, C. Tetrahedron Lett.
2000, 41, 663. (b) Besev, M.; Engman, L. Organic Lett. 2000,
2, 1589.
5. Coates, R. B.; Pigott, H. D.; Ollinger, J. Tetrahedron Lett.

456
C. Miniejew et al. / Tetrahedron 61 (2005) 447–456
1974, 3955. Bates, G. S.; Ramaswamy, S. Can. J. Chem. 1983,
´
61, 2466. De Kimpe, N.; Verhe, R.; De Buyck, L.; Schamp, N.
7. Uemura, S.; Ohe, K. J. Chem. Soc, Perkin Trans. 1 1990, 907.
8. Houllemare, D. Thesis, Rouen, 1997.
´
9. De Kimpe, N.; Verhe, R.; De Buyck, L.; Hasma, H.; Schamp,
Synthesis 1983, 632. Youn, J.-H.; Herrmann, R.; Ugi, I.
Synthesis 1987, 159.
6. Ahlbrecht, H. Tetrahedron Lett. 1972, 44, 4491. De Kimpe,
N. Tetrahedron 1976, 32, 2457. De Kimpe, N.; De Corte, B.;
´
Verhe, R.; De Buyck, L.; Schamp, N. Tetrahedron Lett. 1984,
´
¨
N.; Verhe, R.; De Buyck, L.; Moens, L.; Schamp, N. Synthesis
1982, 43. Moss, N.; Gauthier, J.; Ferland, J.-M. Synlett 1994,
142. Concellon, J. M.; Bernard, P. L.; Riego, E. J. J. Org.
Chem. 2001, 66, 2764.
25, 1095.
10. Miniejew, C.; Outurquin, F.; Pannecoucke, X. Org. Biomol.
Chem. 2004, 2, 1575.