Homoallenyl azines in criss-cross cycloaddition reactions

Article abstract of DOI:10.1007/s00706-012-0865-7

Thermally initiated combined intra-intermolecular criss-cross cycloadditions of substituted nonsymmetrical allenyl azines with isocyanate or isothiocyanate dipolarophiles were investigated. Substituted 1,3,10-triazatricyclo[5.2.1.0^4,10]dec-6-en

Full text of DOI:10.1007/s00706-012-0865-7

Monatsh Chem (2013) 144:205–216
DOI 10.1007/s00706-012-0865-7
ORIGINAL PAPER
Homoallenyl azines in criss-cross cycloaddition reactions
•
Juraj Galeta Stanislav Man Aneta Valouskova
•
•
ˇ
´
´ˇ
Milan Potacek
Received: 10 June 2012 / Accepted: 24 September 2012 / Published online: 7 November 2012
Ó Springer-Verlag Wien 2012
Abstract Thermally initiated combined intra-intermo-
lecular criss-cross cycloadditions of substituted nonsym-
metrical allenyl azines with isocyanate or isothiocyanate
dipolarophiles were investigated. Substituted 1,3,10-triaza-
tricyclo[5.2.1.04,10]dec-6-en-2-ones or -dec-6-ene-2-thiones
were obtained as the main products in moderate to very good
yields. The thermal stabilities of the tricyclic adducts in
reactions with the competing reactive dipolarophile dimethyl
acetylenedicarboxylate were studied and are discussed. In
some cases, substituted 5,6-dihydro-4H-pyrrolo[1,2-b]pyra-
zoles were found as side products. This reaction showed high
atomeconomyandinallcasesweobservedthepresenceofone
diastereoisomer and regioisomer only, which was clearly
revealed by crystallographic analysis.
(Scheme 1) we decided to trap it with reactive hetero-
cumulenes.
Intermolecular 1,3-dipolar cycloaddition between a 1,3-
dipole and an added dipolarophile is an elegant and pow-
erful method for the formation of heterocycles with three
fused five-membered rings [3–5]. Theoretical studies
proved that the whole reaction proceeds as an intra-inter-
molecular and not as an inter-intramolecular process.
Similar applications of nonsymmetrical azines with
substituted alkynes have already been published [6–8].
Moreover, we are even able to prepare bicyclic pyrrolo-
[1,2-b]pyrazoles when no dipolarophile is present or we
can observe their formation as side products in the presence
of less reactive dipolarophiles [3, 4, 8, 9].
In this paper, we conclude our research into reactions of
aromatic allenyl aldazines with isocyanates and isothio-
cyanates and focus on allenyl azines containing an
adamantyl group [10]. The introduction of an adamantane
moiety allows better transport of a molecule through cell
membranes and thereby exerts a favorable effect upon its
biological properties. Derivatives of adamantane have
already found numerous applications in medicinal chem-
istry [11–16] and material science [17–24]. Our method
could serve as one of the easiest and most accessible pro-
cedures for the preparation of heterocyclic compounds
bearing an adamantyl fragment. Besides, heterocycles
bearing pyrrolidinomethyl and morpholinomethyl frag-
ments are also synthesized.
Keywords 1,3-Dipole Á Dipolarophile Á Stereoselective
synthesis Á Heterocycles Á Retro reactions
Introduction
The presence of azine and allene moieties in one molecule
can lead under thermal stress to the formation of new
structures with four fused five-membered rings in so-called
intramolecular criss-cross cycloadditions [1, 2]. Because
such reactions proceed via a 1,3-dipolar intermediate
Electronic supplementary material The online version of this
article (doi:10.1007/s00706-012-0865-7) contains supplementary
material, which is available to authorized users.
Results and discussion
ˇ
´
´ˇ
J. Galeta Á S. Man Á A. Valouskova Á M. Potacek (&)
Department of Chemistry, Faculty of Science,
´ˇ ´
Masaryk University, Kotlarska 2, 611 37 Brno,
Czech Republic
e-mail: potacek@chemi.muni.cz
In our research we initially followed our previous procedure,
in which we introduced and demonstrated a thermally initi-
ated combined intra-intermolecular criss-cros cycloaddition
123

206
J. Galeta et al.
Scheme 1
N N
N N
R2
R2
R1
R2
N
R
R
R1
R
R
N
ΔT
R1
C
R
N N
N N
R2
R2
R1
R1
Table 1 Isolated yields/% and reaction times/h (in parentheses) of two-component cycloaddition reactions of azines 1a–1o with PhNCO
X
H
N
PhNCO
N
O
3
4
2
N
5
N1
10
Xylene
Reflux
N
7
R
C
9
8
6
R
X
1a-1o
2a-2o
R
X
OMe
Me
H
Cl
NO2
H (a–e)
Me (f–j)
Et (k–o)
a
68 (6)
81 (3)a
79 (3)a
71 (6)
85 (3)
84 (3)
64 (6)
91 (3)
72 (3)
62 (6)
81 (3)
73 (3)
81 (3)
82 (0.5)
72 (0.5)
Previously published results [1, 2]
reaction for the first time [3]. Thus, we prepared several
nonsymmetrical allenyl azines (1a–1o) from various
p-substituted benzaldehydes [10] and tested their reac-
tivity in criss-cross cycloadditions with phenylisocyanate
(Table 1). The reactivity strongly depends upon the sub-
stituent R on the allene moiety, where a methyl and ethyl
group could probably facilitate interaction between the
azine and allene parts. This was demonstrated by shorter
reaction time and higher yield. Moreover, electron-with-
drawing groups (EWG) in the aromatic part of the azine
also showed a significant influence on the reaction time.
In addition, the concentration of the reactants plays an
important role and after several optimization steps the
best conditions were characterized by higher dilution
(*30 mmol dm-3) and the presence of a small excess
of phenylisocyanate (10 %). Solvent-free reactions or
microwave initiation afforded either comparable or even
worse yields. The purity of the azines also significantly
affected the resulting purity and yield of cycloadducts 2.
It is worth noting that stopping the reaction before the full
conversion of azines 1a–1d is better than its prolongation,
which always led to an increase in colored impurities and
lower yields only.
The obtained criss-cross products 2 are partially unsat-
urated compounds with three fused five-membered rings.
This reaction was found to be regio- and stereoselective.
We observed one diastereoisomer only as a racemic mix-
ture of two enantiomers differing in the configuration at
stereogenic centers C4 and C9. The formation of the sec-
ond diastereoisomer was never observed (Scheme 2). Such
behavior was not associated just with phenylisocyanate
reactions, but was observed with any kind of dipolarophile.
The relative configurations at the stereogenic centers were
determined by crystallographic measurements.
We repeated the reaction protocol but using phenyliso-
thiocyanate, benzylisocyanate, and benzylisothiocyanate as
dipolarophiles and azines 1k (R = Et, X = OCH3) and 1m
(R = Et, X = H). Beside the expected cycloadducts (2p,
2q, 2r), we observed the formation of substituted 5,6-
dihydro-4H-pyrrolo[1,2-b]pyrazoles 3 as side products in
high quantity (*50 %). This observation can be rational-
ized by the low stability of the formed adducts 2 and low
reactivity of the dipolarophiles. This instability was dem-
onstrated in the competing reaction of cycloadduct 2f
with an excess of the reactive dipolarophile dimethyl
acetylenedicarboxylate (DMAD, 3 equiv.) in refluxing
123

Homoallenyl azines in criss-cross cycloaddition reactions
207
substitution at C9 afforded, under the same conditions, less
than 5 % of product 3. This illustrates the stabilizing effect
of the EWG group upon the formed bicyclic 1,3-dipole,
which then reacts reversibly with released PhNCO rather
than rearranging into compound 3. Yet, when the com-
peting reagent DMAD is added to the reaction with 2j, the
mixture after the reaction contains compounds 2 and 4 in
1:1 ratio, which can be explained by the same reactivity of
1,3-dipole towards DMAD and released PhNCO.
H
N
O
4
N N
9
Ar
H
R
N
C
O
After the analogous competing reaction of cycloadduct
2p from PhNCS (see Fig. 1) in the presence of DMAD, we
observed a significant difference in the composition of the
reaction mixture. The NMR spectrum of the crude reaction
mixture after 3 h showed the presence of the pure cyc-
loadduct 4. However, in the reaction of 2p without a
dipolarophile, we also obtained a very pure spectrum after
4 h but of bicyclic product 3 only. PhNCS was therefore
shown to be a less reactive and, at the same time, more
stable component than the more reactive DMAD. Thus, we
observed the formation of either pure compound 4 or,
without dipolarophile, pure product 3 as a 1,3-dipole
transformation product. This also indicates that the type of
substituent at C9 does not play any important role in
determining the reaction path followed. The preparation of
heterocycles 3 and 4 is discussed elsewhere [3, 4, 6–9].
The colorless or light yellow crystalline solids 2 are
stable at room temperature and we did not observe any
decomposition or any visible changes, even after several
years. Crystal structures of all the presented compounds
were obtained after the slow evaporation of diethyl ether or
acetone solution. Again, we observed the formation of just
one diastereoisomer only (Fig. 1).
N N
Ar
R
H
N
O
4
N N
9
H
Ar
R
Scheme 2
xylene (Scheme 3). After 7 h, we obtained both possible
criss-cross products 2f and 4 in 1:1 ratio. This demonstrates
that the reaction of 1 with isocyanates is reversible. Any
prolongation of the reaction time leads to the production of
either bicyclic products 3 or a mixture of unidentified side
products. In other words, the lower the yield of 2 is, the
higher the yield of 3. When compound 2f was heated for
7 h in xylene, only 25 % of the final mixture was product
3. This lower conversion to product 3 is evidence of the
probability that when compound 2f is heated, its decom-
position proceeds to dipole and PhNCO and ends by
retrocycloaddition. The derivative 2j with p-NO2-Ph
R
R
Ph
Ph
N
R
N
H
C
H
N
Ar
O
O
R
N
ΔT
R
R
PhNCO
N
N
N
N
N
N
C
R = COOMe
Ar
Ar
Ar
1f
2f
4
ΔT
N
N
Ar
3
Scheme 3
123

208
J. Galeta et al.
Fig. 1 ORTEP representations
of cycloadducts 2p (left) and 2r
(right) shown at the 50 %
probability level (blue N, red O,
orange S) (color figure online)
Table 2 Isolated yields/% and reaction times/h (in parentheses) of two-component cycloaddition reactions of azines 5a–5e with PhNCO and
PhNCS
H
N
PhNCX
X
N
3
4
2
5
N
1
10
Xylene
Reflux
N N
7
9
R
C
8
6
R
5a-5e
6a-6j
R
H
Me
Pyrr
Morph
Ad
PhNCO (a–e)
PhNCS (f–j)
75 (8)
50 (5)
65 (2)
55 (2)
76 (2)
55 (2)
60 (2)
50 (2)
31 (4)
14 (4)
Pyrr pyrrolidinomethyl, Morph morpholinomethyl, Ad 1-adamantyl
Fig. 2 ORTEP representations
of cycloadducts 6a (left) and 6k
(right) shown at the 50 %
probability level (blue N, red O)
(color figure online)
Our further attention was devoted to the synthesis of
adamantane-containing heterocycles 6 and, therefore, we
synthesized several allenyl azines 5a–5e for their prepa-
ration (Table 2) [10]. Positive results were obtained in
reactions with isocyanates and isothiocyanates. Not sur-
prisingly, NMR and X-ray measurements confirmed the
formation of one diastereoisomer only (Fig. 2 and Sup-
plementary Material). We isolated stable and very pure
colorless products after crystallization from acetone or
petroleum ether. The uniform yields suggest that the
influence of the adamantyl moiety is negligible and that the
result of the reaction depends exclusively upon the type of
123

Homoallenyl azines in criss-cross cycloaddition reactions
209
Table 3 Overview of stability
Product
DMAD
Reaction time/h
Product 2
Product 3
Product 4
measurements of criss-cross
products with/without DMAD
in refluxing xylene
2f
–
7
7
7
7
4
3
7
7
7
7
75 %
50 %
[95 %
50 %
–
25 %
–
2f
3 equiv.
–
50 %
–
2j
–
\5 %
2j
3 equiv.
–
50 %
–
2p
2p
6b
6b
–
100 %
3 equiv.
–
–
–
100 %
–
90 %
90 %
90 %
90 %
10 %
–
3 equiv.
–
10 %
–
Product with 2 hydrogen
atoms at C9 [4]
10 %
–
3 equiv.
10 %
dipolarophile. The influence of the allenyl part substituent
(R) is reflected almost exclusively by different reaction
times. There is actually just one exception for both dipol-
arophiles, where the formation of tricyclic compounds with
two adamantyl groups (6e and 6j) was suppressed by the
creation of the side product 2,4-di(1-adamantyl)-5,5-
dimethyl-5,6-dihydro-4H-pyrrolo[1,2-b]pyrazole.
adamantyl moiety. The stability of the prepared tricyclic
compounds 2 and 6 was checked in the presence of added
active dipolarophile. The 1,3-dipolar cycloaddition reac-
tion was shown to be reversible. After the reaction we
identified either substituted 5,6-dihydro-4H-pyrrolo[1,2-
b]pyrazoles 3 or, in the presence of reactive DMAD, the
products of retro-1,3-dipolar cycloaddition, namely 1,10-
diazatricyclo[5.2.1.04,10]deca-2,6-dienes 4.
Stability measurements of product 6b without a dipol-
arophile and with added DMAD in refluxing xylene
showed the same results. This means that after 7 h almost
90 % of compound 6b did not change and we observed
only around 10 % of 3-like and 4-like product, respec-
tively. To determine the electronic influence of C9
substitution we used a particular compound containing two
hydrogen atoms at C9 prepared previously [4]. Again, we
obtained around 90 % of unchanged starting material 6 and
about 10 % of by-product 3 or 4. In other words, this
means that the stabilizing or destabilizing effect of p-OMe
(2f) or p-NO2 (2j) substitution is missing and that the
stability of such systems is significantly higher (Table 3).
To demonstrate the diastereoselectivity of the reaction,
we prepared an allenyl azine from 1-adamantyl methyl
ketone and subsequently the appropriate criss-cross product
6k. X-ray structure analysis confirmed our assumption: the
bulky adamantyl group at C9 was again directed towards
one side of the molecule as is the hydrogen atom at C4
(Fig. 2).
Experimental
Dipolarophiles were purchased from commercial suppliers
and used as received. Xylene (mixture of isomers) was
dried and distilled from sodium/benzophenone and stored
˚
over dry 4 A molecular sieves. All reactions were carried
out under a dry argon atmosphere and were monitored by
TLC (Merck F254 silica gel). Products were separated by
preparative TLC or by liquid chromatography with a
Horizon HPFC system (Biotage, Inc.) fitted with a Biotage
Si 25?M column. Melting points were determined in open
capillaries with an MPM-HV2 thermometer. FTIR spectra
were recorded with a GENESIS ATI (Unicam) spectrom-
eter. 1H and 13C NMR spectra were recorded with a Bruker
Avance 500 spectrometer operating at 500.13 MHz (1H)
and 126 MHz (13C) with CDCl3 as solvent. Chemical shifts
are reported in ppm, and tetramethylsilane (d = 0.00 ppm)
and CDCl3 (d = 77.23 ppm) served as internal standards
for 1H NMR and 13C NMR analysis, respectively. MS data
were obtained with a Fisons Instruments TRIO 1000
spectrometer at 70 eV in the EI mode. Elemental analyses
were performed with a Perkin-Elmer CHN 2400 apparatus.
High-resolution mass spectra (HRMS) were recorded on a
Micromass Q-Tof micro instrument in the positive ESI
(CV = 30 V) mode.
Conclusion
The preparation of several substituted 1,3,10-triazatricy-
clo[5.2.1.04,10]dec-6-en-2-ones 2 and -dec-6-ene-2-thiones
6 was investigated. Their formation proceeds through a
bicyclic 1,3-dipolar intermediate. The scope of the reaction
was also tested with several azines containing an ada-
mantyl group. Thus, we introduced a new synthetic
procedure for the preparation of heterocycles bearing an
X-ray diffraction data were collected on a Kuma KM-4
four-circle CCD diffractometer and corrected for Lorentz
and polarization effects. The structures were resolved by
123

210
J. Galeta et al.
3
3
5.37 (dd, J = 8.9 Hz, J = 5.5 Hz, 1H, H9), 5.48 (s, 1H,
H4), 7.12–7.20 (m, 3H, Ph), 7.31–7.38 (m, 4H, Ph), 7.39–
7.47 (m, 2H, Ph) ppm; 13C NMR: d = 21.3 (Ph-CH3), 24.4
(CH3), 27.4 (CH3), 33.5 (C8), 55.1 (C5), 65.5 (C9), 85.1
(C4), 110.2 (C6), 122.5 (2 9 CH), 125.4 (CH), 126.1
(2 9 CH), 129.1 (2 9 CH), 129.5 (2 9 CH), 137.1 (C,
Ph), 139.1 (C, Ph), 140.1 (C, Ph), 149.8 (C7), 161.8 (C2)
direct methods and refined by full-matrix least-squares
methods using the SHELXTL program package [25].
Hydrogen atoms were placed in calculated idealized posi-
tions. The crystal structures of compounds 2p, 2r, 6a, 6g,
6i, 6k, 6m, and 6o (see Supplementary Material) have
been deposited at the Cambridge Crystallographic Data
Centre and allocated the deposition numbers CCDC
875425–875431 and 875881. The CCDC numbers are
shown in the experimental section for each compound
individually.
ꢀ
ppm; IR: m = 3,062, 2,964, 2,921, 2,863, 1,702 (C=O),
1,597, 1,501, 1,408, 1,305, 1,145 cm-1; MS: m/z (%) =
345 (M?, 47), 330 (13), 199 (57), 146 (85), 104 (39), 91
(46), 77 (100).
General procedure for the synthesis of criss-cross
cycloadducts 2 and 6
(4R*,9S*)-5,5-Dimethyl-3,9-diphenyl-1,3,10-triazatricy-
clo[5.2.1.04,10]dec-6-en-2-one (2c, C21H21N3O)
Yield 64 % (6 h); m.p.: 153.5–155.0 °C; 1H NMR:
d = 0.84 (s, 3H, CH3), 1.38 (s, 3H, CH3), 2.63 (ddd,
2J = 15.4 Hz, 3J = 5.4 Hz, 4J = 2.4 Hz, 1H, H8), 3.17
(dd, 2J = 15.4 Hz, 3J = 9.0 Hz, 1H, H8), 4.74 (d,
4J = 2.4 Hz, 1H, H6), 5.41 (dd, 3J = 9.0 Hz,
3J = 5.4 Hz, 1H, H9), 5.49 (s, 1H, H4), 7.14–7.19 (m,
1H, Ph), 7.23–7.28 (m, 1H, Ph), 7.33–7.38 (m, 4H, Ph),
7.42–7.49 (m, 4H, Ph) ppm; 13C NMR: d = 24.4 (CH3),
27.4 (CH3), 33.5 (C8), 55.2 (C5), 65.6 (C9), 85.1 (C4),
110.3 (C6), 122.5 (2 9 CH), 125.5 (CH), 126.2 (2 9 CH),
127.5 (CH), 128.9 (2 9 CH), 129.1 (2 9 CH), 139.1 (C,
Ph), 143.1 (C, Ph), 149.7 (C7), 161.8 (C2) ppm; IR:
A mixture of allenyl azine 1 or 5 (1 mmol) and dipolaro-
phile (1.1 mmol) in 30 cm3 dry xylene was heated under
reflux for the time given for each compound. The solvent
was then removed under vacuum and, in the case of cyc-
loadducts 2, the residue was purified by recrystallization
from EtOH/H2O = 60/40. An analytically pure sample was
obtained after preparative TLC (SiO2, AcOEt/PE = 20/80)
followed by crystallization from Et2O/PE = 1/1. Pure
samples of adamantane-containing heterocycles 6 were
isolated by liquid chromatography (DCM) or by recrys-
tallization from acetone or PE.
ꢀ
m = 3,063, 2,964, 2,924, 2,862, 1,701 (C=O), 1,595, 1,495,
(4R*,9S*)-9-(4-Methoxyphenyl)-5,5-dimethyl-3-phenyl-
1,3,10-triazatricyclo[5.2.1.04,10]dec-6-en-2-one
1,409, 1,304 cm-1; MS: m/z (%) = 331 (M?, 88), 316
(31), 199 (55), 132 (44), 103 (54), 77 (100).
(2a, C22H23N3O2)
Yield 68 % (6 h); m.p.: 157.0–158.0 °C; 1H NMR:
d = 0.84 (s, 3H, CH3), 1.38 (s, 3H, CH3), 2.62 (ddd,
2J = 15.5 Hz, 3J = 5.3 Hz, 4J = 2.0 Hz, 1H, H8), 3.13
(dd, 2J = 15.5 Hz, 3J = 8.9 Hz, 1H, H8), 3.79 (s, 3H,
O-CH3), 4.73 (d, 4J = 2.0 Hz, 1H, H6), 5.35 (dd,
3J = 8.9 Hz, 3J = 5.3 Hz, 1H, H9), 5.47 (s, 1H, H4),
6.89 (d, 3J = 8.6 Hz, 2H, Ph), 7.12–7.22 (m, 1H, Ph),
7.31–7.47 (m, 6H, Ph) ppm; 13C NMR: d = 24.4 (CH3),
27.4 (CH3), 33.5 (C8), 55.1 (C5), 55.5 (O-CH3), 65.3 (C9),
85.1 (C4), 110.2 (C6), 114.2 (2 9 CH), 122.5 (2 9 CH),
125.4 (CH), 127.4 (2 9 CH), 129.1 (2 9 CH), 135.3 (C,
Ph), 139.1 (C, Ph), 149.8 (C7), 159.1 (C, Ph), 161.8 (C2)
ppm; IR: ꢀm = 3,061, 2,965, 2,927, 2,861, 1,704 (C=O),
1,597, 1,508, 1,409, 1,295, 1,245, 1,172, 1,030 cm-1; MS:
m/z (%) = 361 (M?, 38), 345 (25), 199 (44), 162 (100),
134 (21), 77 (35).
(4R*,9S*)-9-(4-Chlorophenyl)-5,5-dimethyl-3-phenyl-
1,3,10-triazatricyclo[5.2.1.04,10]dec-6-en-2-one
(2d, C21H20ClN3O)
Yield 62 % (6 h); m.p.: 148.0–149.5 °C; 1H NMR:
d = 0.84 (s, 3H, CH3), 1.38 (s, 3H, CH3), 2.56 (ddd,
2J = 15.4 Hz, 3J = 5.3 Hz, 4J = 2.0 Hz, 1H, H8), 3.17
(dd, 2J = 15.4 Hz, 3J = 9.0 Hz, 1H, H8), 4.75 (d,
4J = 2.0 Hz, 1H, H6), 5.37 (dd, 3J = 9.0 Hz,
3J = 5.3 Hz, 1H, H9), 5.49 (s, 1H, H4), 7.12–7.20 (m,
1H, Ph), 7.28–7.46 (m, 8H, Ph) ppm; 13C NMR: d = 24.4
(CH3), 27.4 (CH3), 33.5 (C8), 55.2 (C5), 65.0 (C9), 85.1
(C4), 110.6 (C6), 122.6 (2 9 CH), 125.6 (CH), 127.6
(2 9 CH), 129.0 (2 9 CH), 129.2 (2 9 CH), 133.3 (C,
Ph), 139.0 (C, Ph), 141.6 (C, Ph), 149.4 (C7), 161.6 (C2)
ꢀ
ppm; IR: m = 3,059, 2,962, 2,927, 2,862, 1,706 (C=O),
1,596, 1,492, 1,401, 1,302, 1,203, 1,143 cm-1; MS: m/z
(%) = 365 (M?, 30), 350 (12), 199 (42), 166 (46), 104
(33), 96 (44), 77 (100).
(4R*,9S*)-5,5-Dimethyl-9-(4-methylphenyl)-3-phenyl-
1,3,10-triazatricyclo[5.2.1.04,10]dec-6-en-2-one
(2b, C22H23N3O)
Yield 71 % (6 h); m.p.: 126.0–127.5 °C; 1H NMR:
d = 0.84 (s, 3H, CH3), 1.38 (s, 3H, CH3), 2.33 (s, 3H,
Ph-CH3), 2.62 (ddd, 2J = 15.4 Hz, 3J = 5.5 Hz,
4J = 1.8 Hz, 1H, H8), 3.14 (dd, 2J = 15.4 Hz,
3J = 8.9 Hz, 1H, H8), 4.73 (d, 4J = 1.8 Hz, 1H, H6),
(4R*,9S*)-5,5-Dimethyl-9-(4-nitrophenyl)-3-phenyl-
1,3,10-triazatricyclo[5.2.1.04,10]dec-6-en-2-one
(2e, C21H20N4O3)
Yield 81 % (3 h); m.p.: 172.5–173.5 °C; 1H NMR:
d = 0.85 (s, 3H, CH3), 1.39 (s, 3H, CH3), 2.55 (ddd,
123

Homoallenyl azines in criss-cross cycloaddition reactions
211
2J = 15.4 Hz, 3J = 5.3 Hz, 4J = 2.0 Hz, 1H, H8), 3.25
(dd, 2J = 15.4 Hz, 3J = 9.2 Hz, 1H, H8), 4.80 (d,
4J = 2.0 Hz, 1H, H6), 5.48 (dd, 3J = 9.2 Hz,
3J = 5.3 Hz, 1H, H9), 5.52 (s, 1H, H4), 7.17–7.23 (m,
(4R*,9S*)-5,5,6-Trimethyl-3,9-diphenyl-1,3,10-triazatricy-
clo[5.2.1.04,10]dec-6-en-2-one (2h, C22H23N3O)
Yield 91 % (3 h); m.p.: 194.0–196.0 °C; 1H NMR:
d = 0.77 (s, 3H, CH3), 1.31 (s, 3H, CH3), 1.53 (d,
5J = 1.8 Hz, 3H, C6-CH3), 2.53 (ddm, 2J = 15.1 Hz,
3J = 5.3 Hz, 1H, H8), 3.16 (dd, 2J = 15.1 Hz, 3J =
3
1H, Ph), 7.35–7.47 (m, 4H, Ph), 7.63 (d, J = 8.7 Hz, 2H,
Ph), 8.22 (d, 3J = 8.7 Hz, 2H, Ph) ppm; 13C NMR:
d = 24.3 (CH3), 27.4 (CH3), 33.4 (C8), 55.3 (C5), 64.9
(C9), 85.2 (C4), 111.0 (C6), 122.6 (2 9 CH), 124.2
(2 9 CH), 125.8 (CH), 127.1 (2 9 CH), 129.2 (2 9 CH),
138.7 (C, Ph), 147.4 (C, Ph), 148.8 (C7), 150.3 (C, Ph),
3
3
9.0 Hz, 1H, H8), 5.36 (dd, J = 9.0 Hz, J = 5.3 Hz, 1H,
H9), 5.51 (s, 1H, H4), 7.14–7.19 (m, 1H, Ph), 7.23–7.28
(m, 1H, Ph), 7.32–7.38 (m, 4H, Ph), 7.41–7.49 (m, 4H, Ph)
ppm; 13C NMR: d = 8.7 (C6-CH3), 22.1 (CH3), 25.7
(CH3), 32.4 (C8), 55.6 (C5), 65.2 (C9), 84.7 (C4), 116.2
(C6), 122.8 (2 9 CH), 125.5 (CH), 126.2 (2 9 CH), 127.4
(CH), 128.8 (2 9 CH), 129.1 (2 9 CH), 139.2 (C, Ph),
ꢀ
161.4 (C2) ppm; IR: m = 3,052, 2,961, 2,928, 2,863, 1,711
(C=O), 1,599, 1,518, 1,347, 1,294 cm-1
; MS: m/z
(%) = 376 (M?, 100), 361 (47), 199 (23), 104 (31), 96
ꢀ
(43), 77 (59).
143.2 (C, Ph), 143.3 (C7), 162.1 (C2) ppm; IR: m = 3,053,
2,973, 2,934, 2,861, 1,696 (C=O), 1,596, 1,493, 1,409,
1,294 cm-1; MS: m/z (%) = 345 (M?, 37), 250 (18), 104
(43), 77 (100).
(4R*,9S*)-9-(4-Methoxyphenyl)-5,5,6-trimethyl-3-phenyl-
1,3,10-triazatricyclo[5.2.1.04,10]dec-6-en-2-one
(2f, C23H25N3O2)
(4R*,9S*)-9-(4-Chlorophenyl)-5,5,6-trimethyl-3-phenyl-
1,3,10-triazatricyclo[5.2.1.04,10]dec-6-en-2-one
Yield 81 % (3 h); m.p.: 177.0–178.0 °C; 1H NMR:
d = 0.76 (s, 3H, CH3), 1.30 (s, 3H, CH3), 1.52 (d,
5J = 1.7 Hz, 3H, C6-CH3), 2.52 (ddm, 2J = 15.1 Hz,
3J = 5.2 Hz, 1H, H8), 3.12 (dd, 2J = 15.1 Hz, 3J =
8.9 Hz, 1H, H8), 3.79 (s, 3H, O-CH3), 5.30 (dd, 3J =
(2i, C22H22ClN3O)
Yield 81 % (3 h); m.p.: 147.5–148.5 °C; 1H NMR:
d = 0.76 (s, 3H, CH3), 1.30 (s, 3H, CH3), 1.52 (d,
5J = 1.6 Hz, 3H, C6-CH3), 2.46 (ddm, 2J = 15.0 Hz,
3J = 5.2 Hz, 1H, H8), 3.15 (dd, 2J = 15.0 Hz, 3J =
9.0 Hz, 1H, H8), 5.32 (dd, 3J = 9.0 Hz, 3J = 5.2 Hz,
1H, H9), 5.50 (s, 1H, H4), 7.14–7.20 (m, 1H, Ph),
7.29–7.44 (m, 8H, Ph) ppm; 13C NMR: d = 8.6 (C6-
CH3), 22.0 (CH3), 25.6 (CH3), 32.3 (C8), 55.6 (C5), 64.6
(C9), 84.7 (C4), 116.5 (C6), 122.8 (2 9 CH), 125.6 (CH),
127.7 (2 9 CH), 128.9 (2 9 CH), 129.1 (2 9 CH), 133.1
(C, Ph), 139.1 (C, Ph), 141.8 (C, Ph), 142.9 (C7), 162.0
3
8.9 Hz, J = 5.2 Hz, 1H, H9), 5.49 (s, 1H, H4), 6.88 (d,
3J = 8.7 Hz, 2H, Ph), 7.13–7.19 (m, 1H, Ph), 7.32–7.45
(m, 6H, Ph) ppm; 13C NMR: d = 8.6 (C6-CH3), 22.1
(CH3), 25.6 (CH3), 32.3 (C8), 55.5 (C5), 55.5 (O-CH3),
64.8 (C9), 84.7 (C4), 114.2 (2 9 CH), 116.1 (C6), 122.8
(2 9 CH), 125.4 (CH), 127.5 (2 9 CH), 129.1 (2 9 CH),
135.5 (C, Ph), 139.2 (C, Ph), 143.3 (C7), 159.0 (C, Ph),
162.1 (C2) ppm; IR: ꢀm = 3,061, 2,959, 2,924, 2,833, 1,701
(C=O), 1,597, 1,514, 1,410, 1,305, 1,244, 1,182, 1,034
cm-1; MS: m/z (%) = 375 (M?, 35), 280 (26), 162 (100),
134 (21), 77 (35).
ꢀ
(C2) ppm; IR: m = 3,062, 2,969, 2,922, 2,869, 1,704
(C=O), 1,598, 1,490, 1,404, 1,296, 1,221 cm-1; MS:
m/z (%) = 379 (M?, 25), 284 (28), 166 (26), 110 (58),
77 (100).
(4R*,9S*)-5,5,6-Trimethyl-9-(4-methylphenyl)-3-phenyl-
1,3,10-triazatricyclo[5.2.1.04,10]dec-6-en-2-one
(4R*,9S*)-5,5,6-Trimethyl-9-(4-nitrophenyl)-3-phenyl-
1,3,10-triazatricyclo[5.2.1.04,10]dec-6-en-2-one
(2g, C23H25N3O)
Yield 85 % (3 h); m.p.: 161.5–163.0 °C; 1H NMR:
d = 0.76 (s, 3H, CH3), 1.30 (s, 3H, CH3), 1.52 (d,
5J = 1.7 Hz, 3H, C6-CH3), 2.33 (s, 3H, Ph-CH3), 2.53
(ddm, 2J = 15.0 Hz, 3J = 5.2 Hz, 1H, H8), 3.13 (dd,
2J = 15.0 Hz, 3J = 8.9 Hz, 1H, H8), 5.32 (dd,
3J = 8.9 Hz, 3J = 5.2 Hz, 1H, H9), 5.50 (s, 1H, H4),
7.11–7.20 (m, 3H, Ph), 7.32–7.47 (m, 6H, Ph) ppm; 13C
NMR: d = 8.6 (C6-CH3), 21.3 (Ph-CH3), 22.1 (CH3), 25.6
(CH3), 32.3 (C8), 55.5 (C5), 65.1 (C9), 84.7 (C4), 116.1
(C6), 122.7 (2 9 CH), 125.4 (CH), 126.2 (2 9 CH), 129.1
(2 9 CH), 129.5 (2 9 CH), 137.0 (C, Ph), 139.3 (C, Ph),
(2j, C22H22N4O3)
Yield 82 % (0.5 h); m.p.: 151.0–152.0 °C; 1H NMR:
d = 0.78 (s, 3H, CH3), 1.31 (s, 3H, CH3), 1.54 (d,
5J = 1.5 Hz, 3H, C6-CH3), 2.45 (ddm, 2J = 15.1 Hz,
3J = 5.2 Hz, 1H, H8), 3.24 (dd, 2J = 15.1 Hz, 3J =
9.1 Hz, 1H, H8), 5.43 (dd, 3J = 9.1 Hz, 3J = 5.2 Hz,
1H, H9), 5.53 (s, 1H, H4), 7.17–7.22 (m, 1H, Ph), 7.35–
3
7.45 (m, 4H, Ph), 7.64 (d, J = 8.7 Hz, 2H, Ph), 8.21 (d,
3J = 8.7 Hz, 2H, Ph) ppm; 13C NMR: d = 8.7 (C6-CH3),
22.0 (CH3), 25.6 (CH3), 32.3 (C8), 55.7 (C5), 64.5 (C9),
84.8 (C4), 117.1 (C6), 122.9 (2 9 CH), 124.1 (2 9 CH),
125.8 (CH), 127.1 (2 9 CH), 129.2 (2 9 CH), 138.9 (C,
Ph), 142.3 (C7), 147.4 (C, Ph), 150.5 (C, Ph), 161.7 (C2)
ꢀ
140.3 (C, Ph), 143.3 (C7), 162.1 (C2) ppm; IR: m = 3,061,
2,969, 2,918, 2,861, 1,705 (C=O), 1,599, 1,504, 1,406,
1,298 cm-1; MS: m/z (%) = 359 (M?, 41), 344 (12), 264
(51), 231 (25), 146 (62), 110 (42), 91 (47), 77 (100).
ꢀ
ppm; IR: m = 3,064, 2,968, 2,935, 2,863, 1,712 (C=O),
1,600, 1,524, 1,347, 1,290 cm-1; MS: m/z (%) = 390
123

212
J. Galeta et al.
(M?, 100), 375 (37), 295 (41), 271 (29), 197 (31), 110 (42),
77 (80).
(C4), 121.6 (C6), 123.0 (2 9 CH), 125.5 (CH), 126.2
(2 9 CH), 127.4 (CH), 128.8 (2 9 CH), 129.1 (2 9 CH),
139.2 (C, Ph), 143.0 (C, Ph), 143.3 (C7), 162.2 (C2) ppm;
IR: ꢀm = 3,062, 2,965, 2,930, 2,877, 1,701 (C=O), 1,599,
1,504, 1,402, 1,302, 1,229 cm-1; MS: m/z (%) = 359 (M?,
42), 250 (38), 211 (23), 132 (25), 124 (32), 104 (49), 77
(100).
(4R*,9S*)-6-Ethyl-9-(4-methoxyphenyl)-5,5-dimethyl-3-
phenyl-1,3,10-triazatricyclo[5.2.1.04,10]dec-6-en-2-one
(2k, C24H27N3O2)
Yield 79 % (3 h); m.p.: 155.5–156.0 °C; 1H NMR:
d = 0.78 (s, 3H, CH3), 1.07 (t, 3J = 7.6 Hz, 3H, Et),
1.34 (s, 3H, CH3), 1.83–2.10 (m, 2H, Et), 2.59 (ddm,
2J = 15.3 Hz, 3J = 5.0 Hz, 1H, H8), 3.20 (dd, 2J =
15.3 Hz, 3J = 8.9 Hz, 1H, H8), 3.79 (s, 3H, O-CH3),
(4R*,9S*)-9-(4-Chlorophenyl)-6-ethyl-5,5-dimethyl-3-phe-
nyl-1,3,10-triazatricyclo[5.2.1.04,10]dec-6-en-2-one
(2n, C23H24ClN3O)
3
3
5.32 (dd, J = 8.9 Hz, J = 5.0 Hz, 1H, H9), 5.44 (s, 1H,
H4), 6.89 (d, 3J = 8.6 Hz, 2H, Ph), 7.12–7.22 (m, 1H, Ph),
7.30–7.45 (m, 6H, Ph) ppm; 13C NMR: d = 13.8 (Et), 17.7
(Et), 22.3 (CH3), 26.6 (CH3), 32.9 (C8), 55.5 (O-CH3), 55.9
(C5), 64.8 (C9), 84.9 (C4), 114.2 (2 9 CH), 121.5 (C6),
123.0 (2 9 CH), 125.5 (CH), 127.5 (2 9 CH), 129.1
(2 9 CH), 135.5 (C, Ph), 139.3 (C, Ph), 143.1 (C7),
Yield 73 % (3 h); m.p.: 146.0–147.0 °C; 1H NMR:
d = 0.78 (s, 3H, CH3), 1.07 (t, 3J = 7.6 Hz, 3H, Et),
1.34 (s, 3H, CH3), 1.83–2.07 (m, 2H, Et), 2.52 (ddm,
2J = 15.3 Hz, 3J = 5.1 Hz, 1H, H8), 3.24 (dd, 2J =
15.3 Hz, 3J = 9.0 Hz, 1H, H8), 5.33 (dd, 3J = 9.0 Hz,
3J = 5.1 Hz, 1H, H9), 5.45 (s, 1H, H4), 7.13–7.20 (m, 1H,
Ph), 7.28–7.48 (m, 8H, Ph) ppm; 13C NMR: d = 13.8 (Et),
17.7 (Et), 22.3 (CH3), 26.6 (CH3), 32.9 (C8), 56.0 (C5),
64.6 (C9), 85.0 (C4), 121.9 (C6), 123.0 (2 9 CH), 125.7
(CH), 127.7 (2 9 CH), 128.9 (2 9 CH), 129.1 (2 9 CH),
133.2 (C, Ph), 139.1 (C, Ph), 141.8 (C, Ph), 142.7 (C7),
ꢀ
159.0 (C, Ph), 162.2 (C2) ppm; IR: m = 3,061, 2,965,
2,929, 2,864, 1,709 (C=O), 1,597, 1,506, 1,387, 1,296,
1,167, 1,027 cm-1; MS: m/z (%) = 389 (M?, 23), 280
(35), 162 (100), 134 (43), 77 (80).
ꢀ
162.1 (C2) ppm; IR: m = 3,067, 2,968, 2,928, 2,879, 1,702
(4R*,9S*)-6-Ethyl-5,5-dimethyl-9-(4-methylphenyl)-3-phe-
nyl-1,3,10-triazatricyclo[5.2.1.04,10]dec-6-en-2-one
(2l, C24H27N3O)
(C=O), 1,599, 1,492, 1,402, 1,300, 1,226 cm-1; MS:
m/z (%) = 393 (M?, 25), 284 (29), 166 (27), 124 (44),
104 (35), 77 (100).
Yield 84 % (3 h); m.p.: 143.5–145.0 °C; 1H NMR:
d = 0.78 (s, 3H, CH3), 1.06 (t, 3J = 7.6 Hz, 3H, Et),
1.34 (s, 3H, CH3), 1.83–2.10 (m, 2H, Et), 2.33 (s, 3H, Ph-
CH3), 2.58 (ddm, 2J = 15.1 Hz, 3J = 5.1 Hz, 1H, H8),
(4R*,9S*)-6-Ethyl-5,5-dimethyl-9-(4-nitrophenyl)-3-phe-
nyl-1,3,10-triazatricyclo[5.2.1.04,10]dec-6-en-2-one
(2o, C23H24N4O3)
2
3
3.21 (dd, J = 15.1 Hz, J = 8.9 Hz, 1H, H8), 5.34 (dd,
3J = 8.9 Hz, 3J = 5.1 Hz, 1H, H9), 5.45 (s, 1H, H4),
7.11–7.22 (m, 3H, Ph), 7.30–7.46 (m, 6H, Ph) ppm; 13C
NMR: d = 13.8 (Et), 17.7 (Et), 21.3 (Ph-CH3), 22.3 (CH3),
26.6 (CH3), 32.9 (C8), 56.0 (C5), 65.1 (C9), 84.9 (C4),
121.5 (C6), 123.0 (2 9 CH), 125.5 (CH), 126.2 (2 9 CH),
129.1 (2 9 CH), 129.4 (2 9 CH), 137.0 (C, Ph), 139.3 (C,
Ph), 140.3 (C, Ph), 143.1 (C7), 162.2 (C2) ppm; IR:
Yield 72 % (0.5 h); m.p.: 146.5–147.5 °C; 1H NMR:
d = 0.79 (s, 3H, CH3), 1.08 (t, 3J = 7.6 Hz, 3H, Et),
1.35 (s, 3H, CH3), 1.90–2.07 (m, 2H, Et), 2.51 (ddm,
2J = 15.2 Hz, 3J = 5.1 Hz, 1H, H8), 3.32 (dd, 2J =
15.2 Hz, 3J = 9.2 Hz, 1H, H8), 5.45 (dd, 3J = 9.2 Hz,
3J = 5.1 Hz, 1H, H9), 5.48 (s, 1H, H4), 7.17–7.22 (m, 1H,
Ph), 7.35–7.44 (m, 4H, Ph), 7.64 (d, 3J = 8.7 Hz, 2H, Ph),
8.21 (d, J = 8.7 Hz, 2H, Ph) ppm; 13C NMR: d = 13.7
3
ꢀ
m = 3,066, 2,963, 2,932, 2,871, 1,710 (C=O), 1,598, 1,495,
(Et), 17.7 (Et), 22.2 (CH3), 26.6 (CH3), 32.8 (C8), 56.1
(C5), 64.5 (C9), 85.1 (C4), 122.5 (C6), 123.1 (2 9 CH),
124.1 (2 9 CH), 125.9 (CH), 127.1 (2 9 CH), 129.2
(2 9 CH), 138.9 (C, Ph), 142.1 (C7), 147.4 (C, Ph),
1,387, 1,302, 1,213 cm-1; MS: m/z (%) = 373 (M?, 36),
358 (11), 264 (55), 146 (47), 124 (35), 104 (35), 91 (53), 77
(100).
ꢀ
150.5 (C, Ph), 161.9 (C2) ppm; IR: m = 3,068, 2,973,
(4R*,9S*)-6-Ethyl-5,5-dimethyl-3,9-diphenyl-1,3,10-triaza-
tricyclo[5.2.1.04,10]dec-6-en-2-one (2m, C23H25N3O)
Yield 72 % (3 h); m.p.: 132.0–133.0 °C; 1H NMR:
d = 0.78 (s, 3H, CH3), 1.07 (t, 3J = 7.6 Hz, 3H, Et),
1.34 (s, 3H, CH3), 1.88–2.06 (m, 2H, Et), 2.59 (ddm,
2J = 15.3 Hz, 3J = 5.1 Hz, 1H, H8), 3.24 (dd,
2J = 15.3 Hz, 3J = 9.0 Hz, 1H, H8), 5.37 (dd,
3J = 9.0 Hz, 3J = 5.1 Hz, 1H, H9), 5.46 (s, 1H, H4),
7.14–7.19 (m, 1H, Ph), 7.22–7.27 (m, 1H, Ph), 7.32–7.50
(m, 8H, Ph) ppm; 13C NMR: d = 13.8 (Et), 17.7 (Et), 22.3
(CH3), 26.6 (CH3), 32.9 (C8), 56.0 (C5), 65.2 (C9), 85.0
2,931, 2,867, 1,708 (C=O), 1,599, 1,518, 1,349,
1,301 cm-1; MS: m/z (%) = 404 (M?, 29), 295 (16), 285
(35), 256 (35), 124 (40), 104 (53), 77 (100).
(4R*,9S*)-6-Ethyl-5,5-dimethyl-3,9-diphenyl-1,3,10-triaza-
tricyclo[5.2.1.04,10]dec-6-ene-2-thione (2p, C23H25N3S)
Yield 54 % (2 h); m.p.: 127.5–128.5 °C; 1H NMR:
d = 0.74 (s, 3H, CH3), 1.09 (t, 3J = 7.6 Hz, 3H, Et),
1.30 (s, 3H, CH3), 1.87–2.09 (m, 2H, Et), 2.71 (ddm,
2J = 15.3 Hz, 3J = 4.7 Hz, 1H, H8), 3.29 (dd,
2J = 15.3 Hz, 3J = 9.0 Hz, 1H, H8), 5.39 (s, 1H, H4),
123

Homoallenyl azines in criss-cross cycloaddition reactions
213
3
3
5.88 (dd, J = 9.0 Hz, J = 4.7 Hz, 1H, H9), 7.23–7.56
(m, 10H, Ph) ppm; 13C NMR: d = 13.7 (Et), 17.5 (Et),
22.0 (CH3), 27.4 (CH3), 32.5 (C8), 56.6 (C5), 69.0 (C9),
90.5 (C4), 121.4 (C6), 126.3 (2 9 CH), 127.2 (2 9 CH),
127.6 (CH), 127.8 (CH), 128.9 (2 9 CH), 129.1 (2 9 CH),
140.1 (C, Ph), 141.7 (C, Ph), 142.4 (C7), 188.0 (C2) ppm;
IR: ꢀm = 3,050, 2,972, 2,919, 2,887, 2,830, 1,706, 1,601,
1,503, 1,401, 1,315, 1,272, 1,211, 1,187, 1,106, 1,099,
1,048 cm-1; MS: m/z (%) = 375 (M?, 57), 360 (14), 301
(19), 240 (81), 225 (30), 211 (47), 163 (17), 148 (19), 137
(34), 122 (49), 109 (52), 91 (32), 77 (100); HRMS:
m/z calcd. for C23H26N3S? 376.1842, found 376.1847;
CCDC number 875425.
2,964, 2,956, 2,930, 2,873, 2,835, 1,609, 1,514, 1,446,
1,315, 1,249, 1,177, 1,029 cm-1; MS: m/z (%) = 420 (M?,
4), 419 (15), 255 (11), 194 (17), 178 (52), 148 (20), 121
(25), 91 (100); HRMS: m/z calcd. for C25H30N3OS?
420.2104, found 420.2113; CCDC number 875426.
(4R*,9R*)-9-(1-Adamantyl)-5,5-dimethyl-3-phenyl-1,3,10-
triazatricyclo[5.2.1.04,10]dec-6-en-2-one
(6a, C25H31N3O)
Yield 75 % (8 h); m.p.: 202.0–203.0 °C; 1H NMR:
d = 0.81 (s, 3H, CH3), 1.35 (s, 3H, CH3), 1.54–1.59 (m,
3H, Ad), 1.63–1.74 (m, 9H, Ad), 1.99–2.03 (m, 3H, Ad),
2
3
2.42 (dd, J = 15.1 Hz, J = 8.7 Hz, 1H, H8), 2.55 (ddd,
2J = 15.1 Hz, 3J = 6.6 Hz, 4J = 2.3 Hz, 1H, H8), 3.78
(dd, 3J = 8.7 Hz, 3J = 6.6 Hz, 1H, H9), 4.65 (d,
4J = 2.3 Hz, 1H, H6), 5.41 (s, 1H, H4), 7.11–7.15 (m,
1H, Ph), 7.31–7.36 (m, 2H, Ph), 7.41–7.45 (m, 2H, Ph)
ppm; 13C NMR: d = 23.9 (C8), 24.4 (CH3), 27.7 (CH3),
28.4 (CH), 35.9 (C9-C), 37.3 (CH2), 38.7 (CH2), 54.9 (C5),
73.4 (C9), 84.7 (C4), 109.9 (C6), 121.9 (2 9 CH), 125.0
(CH), 128.9 (2 9 CH), 139.3 (C, Ph), 150.1 (C7), 162.8
(4R*,9S*)-3-Benzyl-6-ethyl-9-(4-methoxyphenyl)-5,5-
dimethyl-1,3,10-triazatricyclo[5.2.1.04,10]dec-6-en-2-one
(2q, C25H29N3O2)
Yield 23 % (2.5 h); m.p.: 113.0–113.5 °C; 1H NMR:
d = 1.06 (t, 3J = 7.6 Hz, 3H, Et), 1.18 (s, 3H, CH3),
1.21 (s, 3H, CH3), 1.88–2.03 (m, 2H, Et), 2.51 (ddm,
2J = 15.2 Hz, 3J = 5.0 Hz, 1H, H8), 3.12 (dd,
2J = 15.2 Hz, 3J = 8.8 Hz, 1H, H8), 3.78 (s, 3H,
O-CH3), 4.04 (d, 2J = 15.5 Hz, 1H, Ph-CH2), 4.39 (s,
ꢀ
(C2) ppm; IR: m = 2,963, 2,908, 2,850, 1,708 (C=O),
1,599, 1,501, 1,456, 1,384, 1,299, 1,144, 1,074,
1,027 cm-1; MS: m/z (%) = 389 (M?, 93), 374 (59), 199
(22), 135 (100), 119 (17), 104 (21), 93 (24), 77 (34), 67
(19); CCDC number 875427.
2
1H, H4), 5.03 (d, J = 15.5 Hz, 1H, Ph-CH2), 5.24 (dd,
3J = 8.8 Hz, J = 5.0 Hz, 1H, H9), 6.87 (d, J = 8.6 Hz,
2H, Ph), 7.18–7.42 (m, 7H, Ph) ppm; 13C NMR: d = 13.8
(Et), 17.7 (Et), 22.0 (CH3), 26.4 (CH3), 32.9 (C8), 48.2
(Ph-CH2), 55.3 (C5), 55.5 (O-CH3), 64.3 (C9), 84.3 (C4),
114.1 (2 9 CH), 121.1 (C6), 127.6 (2 9 CH), 128.0 (CH),
128.5 (2 9 CH), 129.0 (2 9 CH), 135.7 (C, Ph), 135.9 (C,
Ph), 143.5 (C7), 159.0 (C, Ph), 164.8 (C2) ppm; IR:
3
3
(4R*,9R*)-9-(1-Adamantyl)-5,5,6-trimethyl-3-phenyl-
1,3,10-triazatricyclo[5.2.1.04,10]dec-6-en-2-one
(6b, C26H33N3O)
Yield 65 % (2 h); m.p.: 204.0–206.0 °C; 1H NMR:
d = 0.74 (s, 3H, CH3), 1.27 (s, 3H, CH3), 1.49 (d,
5J = 1.1 Hz, 3H, C6-CH3), 1.54–1.60 (m, 3H, Ad), 1.63–
1.74 (m, 9H, Ad), 1.99–2.03 (m, 3H, Ad), 2.40 (dd,
2J = 14.8 Hz, 3J = 8.5 Hz, 1H, H8), 2.46 (ddm, 2J =
14.8 Hz, 3J = 6.7 Hz, 1H, H8), 3.72 (dd, 3J = 8.5 Hz,
3J = 6.7 Hz, 1H, H9), 5.44 (s, 1H, H4), 7.11–7.15 (m, 1H,
Ph), 7.31–7.36 (m, 2H, Ph), 7.40–7.44 (m, 2H, Ph) ppm;
13C NMR: d = 8.5 (C6-CH3), 22.0 (CH3), 22.7 (C8), 25.9
(CH3), 28.4 (CH), 35.9 (C9-C), 37.3 (CH2), 38.8 (CH2),
55.4 (C5), 72.9 (C9), 84.2 (C4), 115.5 (C6), 122.2
(2 9 CH), 125.0 (CH), 128.9 (2 9 CH), 139.4 (C, Ph),
ꢀ
m = 3,061, 3,029, 2,960, 2,929, 2,871, 2,836, 1,704 (C=O),
1,611, 1,511, 1,247, 1,175, 1,030 cm-1
; MS: m/z
(%) = 403 (M?, 38), 333 (23), 231 (45), 91 (100); HRMS:
?
m/z calcd. for C25H30N3O2 404.2333, found 404.2343.
(4R*,9S*)-3-Benzyl-6-ethyl-9-(4-methoxyphenyl)-5,5-
dimethyl-1,3,10-triazatricyclo[5.2.1.04,10]dec-6-ene-2-thi-
one (2r, C25H29N3OS)
Yield 23 % (2.5 h); m.p.: 129.0–129.5 °C; 1H NMR:
d = 1.07 (t, 3J = 7.6 Hz, 3H, Et), 1.20 (s, 3H, CH3),
1.26 (s, 3H, CH3), 1.86–2.10 (m, 2H, Et), 2.64 (ddm,
2J = 15.2 Hz, 3J = 5.1 Hz, 1H, H8), 3.16 (dd,
2J = 15.2 Hz, 3J = 9.0 Hz, 1H, H8), 3.79 (s, 3H,
O-CH3), 4.29 (d, 2J = 15.0 Hz, 1H, Ph-CH2), 4.50 (s,
1H, H4), 5.81 (dd, 3J = 9.0 Hz, 3J = 5.1 Hz, 1H, H9),
5.84 (d, 2J = 15.0 Hz, 1H, Ph-CH2), 6.89 (d, 3J = 8.6 Hz,
ꢀ
143.7 (C7), 163.2 (C2) ppm; IR: m = 2,966, 2,930, 2,885,
2,849, 1,700 (C=O), 1,601, 1,503, 1,447, 1,401, 1,338,
1,302, 1,242, 1,222, 1,147, 1,121, 1,056, 1,012 cm-1; MS:
m/z (%) = 403 (M?, 48), 388 (31), 308 (17), 149 (100),
135 (27), 93 (16), 77 (24).
3
2H, Ph), 7.26–7.36 (m, 5H, Ph), 7.42 (d, J = 8.6 Hz, 2H,
Ph) ppm; 13C NMR: d = 13.7 (Et), 17.6 (Et), 22.1 (CH3),
27.3 (CH3), 32.4 (C8), 51.5 (Ph-CH2), 55.6 (O-CH3), 56.4
(C5), 67.4 (C9), 87.6 (C4), 114.3 (2 9 CH), 121.0 (C6),
127.8 (2 9 CH), 128.2 (CH), 128.5 (2 9 CH), 129.1
(2 9 CH), 134.6 (C, Ph), 135.1 (C, Ph), 142.3 (C7),
(4R*,9R*)-9-(1-Adamantyl)-5,5-dimethyl-3-phenyl-6-(pyr-
rolidinomethyl)-1,3,10-triazatricyclo[5.2.1.04,10]dec-6-en-
2-one (6c, C30H40N4O)
Yield 76 % (2 h); m.p.: 191.5–192.0 °C; 1H NMR:
d = 0.81 (s, 3H, CH3), 1.39 (s, 3H, CH3), 1.54–1.60 (m,
3H, Ad), 1.63–1.75 (m, 13H, Ad ? Pyrr), 1.99–2.03 (m,
ꢀ
159.2 (C, Ph), 188.4 (C2) ppm; IR: m = 3,058, 3,029,
123

214
J. Galeta et al.
3H, Ad), 2.33–2.49 (m, 5H, H8 ? Pyrr), 2.55 (dd,
2J = 15.0 Hz, 3J = 8.5 Hz, 1H, H8), 2.80 (d, 2J =
13.3 Hz, 1H, C6-CH2), 3.11 (d, 2J = 13.3 Hz, 1H,
(C7), 163.9 (C2) ppm; IR: ꢀm = 2,960, 2,929, 2,893, 2,850,
1,701 (C=O), 1,605, 1,511, 1,423, 1,399, 1,367, 1,280,
1,245, 1,226, 1,186, 1,111, 1,029 cm-1; MS: m/z (%) =
523 (M?, 21), 404 (24), 269 (100), 135 (55).
3
3
C6-CH2), 3.72 (dd, J = 8.5 Hz, J = 6.9 Hz, 1H, H9),
5.39 (s, 1H, H4), 7.11–7.16 (m, 1H, Ph), 7.30–7.35 (m, 2H,
Ph), 7.38–7.42 (m, 2H, Ph) ppm; 13C NMR: d = 22.0
(CH3), 22.9 (C8), 23.8 (CH2, Pyrr), 26.9 (CH3), 28.4 (CH),
35.9 (C9-C), 37.3 (CH2), 38.8 (CH2), 51.1 (C6-CH2), 54.6
(CH2, Pyrr), 55.5 (C5), 73.0 (C9), 85.0 (C4), 117.7 (C6),
122.5 (2 9 CH), 125.2 (CH), 128.9 (2 9 CH), 139.4 (C,
(4R*,9R*)-9-(1-Adamantyl)-5,5-dimethyl-3-phenyl-1,3,10-
triazatricyclo[5.2.1.04,10]dec-6-ene-2-thione
(6f, C25H31N3S)
Yield 50 % (5 h); m.p.: 197.5–200.0 °C; 1H NMR:
d = 0.75 (s, 3H, CH3), 1.28 (s, 3H, CH3), 1.62–1.77 (m,
2
12H, Ad), 1.99–2.07 (m, 3H, Ad), 2.47 (dd, J = 15.5 Hz,
ꢀ
Ph), 146.7 (C7), 163.3 (C2) ppm; IR: m = 2,966, 2,851,
3J = 8.8 Hz, 1H, H8), 2.63 (ddd, 2J = 15.5 Hz, 3J =
5.4 Hz, 4J = 2.2 Hz, 1H, H8), 4.34 (dd, 3J = 8.8 Hz,
3J = 5.4 Hz, 1H, H9), 4.66 (d, 4J = 2.2 Hz, 1H, H6), 5.31
(s, 1H, H4), 7.24–7.32 (m, 1H, Ph), 7.37–7.48 (m, 4H, Ph)
ppm; 13C NMR: d = 23.8 (C8), 23.9 (CH3), 28.3 (CH3),
28.4 (CH), 36.4 (C9-C), 37.2 (CH2), 39.0 (CH2), 55.7 (C5),
76.5 (C9), 90.0 (C4), 109.0 (C6), 127.2 (2 9 CH), 127.5
(CH), 128.9 (2 9 CH), 140.2 (C, Ph), 149.1 (C7), 188.6
2,781, 2,757, 2,729, 1,702 (C=O), 1,597, 1,503, 1,459,
1,402, 1,378, 1,302, 1,263, 1,240, 1,151, 1,111, 1,051,
1,012 cm-1; MS: m/z (%) = 472 (M?, 28), 457 (13), 402
(21), 337 (100), 283 (14), 218 (36), 164 (28), 147 (50), 135
(41), 107 (16), 84 (46), 70 (29).
(4R*,9R*)-9-(1-Adamantyl)-5,5-dimethyl-6-(morpholino-
methyl)-3-phenyl-1,3,10-triazatricyclo[5.2.1.04,10]dec-6-
en-2-one (6d, C30H40N4O2)
ꢀ
(C2) ppm; IR: m = 2,963, 2,906, 2,849, 1,679, 1,597,
Yield 60 % (2 h); m.p.: 210.5–211.0 °C; 1H NMR:
d = 0.81 (s, 3H, CH3), 1.39 (s, 3H, CH3), 1.54–1.60 (m,
3H, Ad), 1.63–1.75 (m, 9H, Ad), 1.99–2.04 (m, 3H, Ad),
2.22–2.33 (m, 2H, N-CH2), 2.38–2.45 (m, 2H, N-CH2),
1,499, 1,455, 1,403, 1,302, 1,256, 1,047 cm-1; MS:
m/z (%) = 405 (M?, 18), 390 (16), 270 (20), 135 (100),
77 (15).
(4R*,9R*)-9-(1-Adamantyl)-5,5,6-trimethyl-3-phenyl-
1,3,10-triazatricyclo[5.2.1.04,10]dec-6-ene-2-thione
(6g, C26H33N3S)
2
3
2.45 (ddm, J = 15.2 Hz, J = 6.6 Hz, 1H, H8), 2.52 (d,
2J = 15.2 Hz, 3J = 8.4 Hz, 1H, H8), 2.75 (d, 2J =
13.3 Hz, 1H, C6-CH2), 2.95 (d, 2J = 13.3 Hz, 1H,
C6-CH2), 3.61–3.70 (m, 4H, O-CH2), 3.73 (dd, 3J =
8.4 Hz, 3J = 6.6 Hz, 1H, H9), 5.40 (s, 1H, H4), 7.12–7.17
(m, 1H, Ph), 7.31–7.41 (m, 4H, Ph) ppm; 13C NMR:
d = 21.9 (CH3), 22.8 (C8), 26.9 (CH3), 28.4 (CH), 35.9
(C9-C), 37.3 (CH2), 38.7 (CH2), 54.0 (C6-CH2), 54.0 (N-
CH2), 55.5 (C5), 67.2 (O-CH2), 72.9 (C9), 85.0 (C4), 115.3
(C6), 122.5 (2 9 CH), 125.3 (CH), 129.0 (2 9 CH), 139.2
Yield 55 % (2 h); m.p.: 196.0–196.5 °C; 1H NMR:
d = 0.68 (s, 3H, CH3), 1.20 (s, 3H, CH3), 1.50 (d,
5J = 1.6 Hz, 3H, C6-CH3), 1.64–1.75 (m, 12H, Ad),
2.00–2.05 (m, 3H, Ad), 2.45 (dd, 2J = 15.2 Hz, 3J =
2
3
8.7 Hz, 1H, H8), 2.53 (ddm, J = 15.2 Hz, J = 5.4 Hz,
1H, H8), 4.29 (dd, 3J = 8.7 Hz, 3J = 5.4 Hz, 1H, H9),
5.32 (s, 1H, H4), 7.26–7.30 (m, 1H, Ph), 7.37–7.45 (m, 4H,
Ph) ppm; 13C NMR: d = 8.2 (C6-CH3), 21.8 (CH3), 22.7
(C8), 26.5 (CH3), 28.4 (CH), 36.4 (C9-C), 37.2 (CH2), 39.1
(CH2), 56.0 (C5), 76.0 (C9), 89.8 (C4), 115.0 (C6), 127.4
(2 9 CH), 127.5 (CH), 128.9 (2 9 CH), 140.4 (C, Ph),
ꢀ
(C, Ph), 148.3 (C7), 163.2 (C2) ppm; IR: m = 2,935, 2,886,
2,853, 2,811, 2,789, 1,699 (C=O), 1,599, 1,503, 1,455,
1,402, 1,379, 1,346, 1,303, 1,217, 1,149, 1,119, 1,031
cm-1; MS: m/z (%) = 488 (M?, 46), 473 (48), 402 (24),
353 (100), 283 (24), 234 (42), 180 (31), 166 (75), 147 (78),
135 (52), 100 (40), 93 (17), 79 (18).
ꢀ
142.5 (C7), 188.8 (C2) ppm; IR: m = 2,967, 2,921, 2,897,
2,846, 1,716, 1,596, 1,498, 1,452, 1,403, 1,335, 1,299,
1,261, 1,213, 1,187, 1,119, 1,085, 1,024 cm-1; MS:
m/z (%) = 419 (M?, 18), 404 (15), 284 (32), 149 (100);
CCDC number 875428.
(4R*,9R*)-6,9-Di-(1-adamantyl)-5,5-dimethyl-3-phenyl-
1,3,10-triazatricyclo[5.2.1.04,10]dec-6-en-2-one
(6e, C35H45N3O)
Yield 31 % (4 h); 1H NMR: d = 0.98 (s, 3H, CH3), 1.41 (s,
(4R*,9R*)-9-(1-Adamantyl)-5,5-dimethyl-3-phenyl-6-(pyr-
rolidinomethyl)-1,3,10-triazatricyclo[5.2.1.04,10]dec-6-
ene-2-thione (6h, C30H40N4S)
2
3H, CH3), 1.53–2.05 (m, 30H, 2 9 Ad), 2.59 (dd, J =
3
2
15.5 Hz, J = 6.0 Hz, 1H, H8), 2.73 (dd, J = 15.5 Hz,
3J = 8.8 Hz, 1H, H8), 3.70 (dd, 3J = 8.8 Hz, 3J = 6.0 Hz,
1H, H9), 5.16 (s, 1H, H4), 7.14–7.19 (m, 1H, Ph), 7.30–
7.36 (m, 4H, Ph) ppm; 13C NMR: d = 25.0 (CH3), 26.2
(C8), 28.4 (CH), 28.9 (CH), 29.0 (CH3), 35.8 (C9-C), 36.5
(C6-C), 37.0 (CH2), 37.3 (CH2), 38.8 (CH2), 42.6 (CH2),
57.1 (C5), 72.2 (C9), 86.2 (C4), 124.2 (2 9 CH), 125.8
(CH), 126.3 (C6), 129.0 (2 9 CH), 139.8 (C, Ph), 144.0
Yield 55 % (2 h); m.p.: 188.5–190.0 °C; 1H NMR:
d = 0.75 (s, 3H, CH3), 1.32 (s, 3H, CH3), 1.60–1.77 (m,
16H, Ad ? Pyrr), 1.99–2.07 (m, 3H, Ad), 2.30–2.60 (m,
6H, Pyrr ? H8), 2.80 (d, 2J = 13.3 Hz, 1H, C6-CH2), 3.11
(d, 2J = 13.3 Hz, 1H, C6-CH2), 4.30 (dd, 3J = 8.0 Hz,
3J = 6.2 Hz, 1H, H9), 5.27 (s, 1H, H4), 7.23–7.33 (m, 1H,
Ph), 7.37–7.44 (m, 4H, Ph) ppm; 13C NMR: d = 21.7
123

Homoallenyl azines in criss-cross cycloaddition reactions
215
(CH3), 22.9 (C8), 23.8 (CH2, Pyrr), 27.5 (CH3), 28.4 (CH),
36.3 (C9-C), 37.2 (CH2), 39.1 (CH2), 50.8 (C6-CH2), 54.6
(CH2, Pyrr), 56.1 (C5), 76.0 (C9), 90.5 (C4), 117.1 (C6),
127.4 (2 9 CH), 127.5 (CH), 128.9 (2 9 CH), 140.4 (C,
2J = 14.3 Hz, 1H, H8), 3.02 (d, 2J = 13.0 Hz, 1H,
C6-CH2), 3.60–3.74 (m, 4H, O-CH2), 5.33 (s, 1H, H4),
7.11–7.17 (m, 1H, Ph), 7.31–7.41 (m, 4H, Ph) ppm; 13C
NMR: d = 19.1 (CH3), 21.8 (CH3), 27.5 (CH3), 28.6 (CH),
33.5 (C8), 36.9 (CH2), 37.2 (CH2), 39.2 (C9-C), 53.8 (C6-
CH2), 54.0 (N-CH2), 55.6 (C5), 67.2 (O-CH2), 77.1 (C9),
83.5 (C4), 122.7 (2 9 CH), 125.1 (CH), 128.9 (2 9 CH),
ꢀ
Ph), 145.5 (C7), 189.1 (C2) ppm; IR: m = 3,020, 2,975,
2,910, 2,851, 1,711, 1,600, 1,418, 1,364, 1,219,
1,047 cm-1; MS: m/z (%) = 488 (M?, 23), 353 (46), 283
(40), 218 (100), 147 (69), 135 (39), 93 (15), 72 (21).
ꢀ
139.4 (C, Ph), 159.5 (C2) ppm; IR: m = 2,934, 2,899,
2,850, 2,807, 2,764, 1,714 (C=O), 1,599, 1,501, 1,454,
1,379, 1,342, 1,293, 1,196, 1,163, 1,118, 1,006 cm-1; MS:
m/z (%) = 502 (M?, 44), 417 (18), 367 (100), 282 (24),
248 (29), 180 (24), 161 (85), 135 (64), 100 (54), 93 (37), 79
(37); HRMS: m/z calcd. for C31H43N4O2? 503.3381, found
503.3396; CCDC number 875429.
(4R*,9R*)-9-(1-Adamantyl)-5,5-dimethyl-6-(morpholino-
methyl)-3-phenyl-1,3,10-triazatricyclo[5.2.1.04,10]dec-6-
ene-2-thione (6i, C30H40N4OS)
Yield 50 % (2 h); m.p.: 210.0–211.0 °C; 1H NMR:
d = 0.75 (s, 3H, CH3), 1.32 (s, 3H, CH3), 1.62–1.76 (m,
12H, Ad), 1.99–2.07 (m, 3H, Ad), 2.21–2.57 (m, 6H,
2
H8 ? N-CH2), 2.76 (d, J = 13.3 Hz, 1H, C6-CH2), 2.94
(d, 2J = 13.3 Hz, 1H, C6-CH2), 3.59–3.71 (m, 4H, O-
(4R*,9R*)-9-(1-Adamantyl)-3-benzyl-5,5-dimethyl-1,3,10-
triazatricyclo[5.2.1.04,10]dec-6-en-2-one
(6l, C26H33N3O)
3
CH2), 4.31 (t, J = 6.9 Hz, 1H, H9), 5.28 (s, 1H, H4),
7.24–7.33 (m, 1H, Ph), 7.35–7.44 (m, 4H, Ph) ppm; 13C
NMR: d = 21.6 (CH3), 22.8 (C8), 27.5 (CH3), 28.4 (CH),
36.3 (C9-C), 37.2 (CH2), 39.0 (CH2), 53.7 (C6-CH2), 53.9
(N-CH2), 56.0 (C5), 67.2 (O-CH2), 76.0 (C9), 90.5 (C4),
114.8 (C6), 127.4 (2 9 CH), 127.6 (CH), 129.0 (2 9 CH),
Yield 31 % (5 h); m.p.: 163.0–165.0 °C; 1H NMR:
d = 1.17 (s, 3H, CH3), 1.20 (s, 3H, CH3), 1.50–1.75 (m,
2
12H, Ad), 1.96–2.05 (m, 3H, Ad), 2.34 (dd, J = 15.2 Hz,
3J = 8.7 Hz, 1H, H8), 2.49 (ddd, 2J = 15.2 Hz, 3J =
6.5 Hz, 4J = 2.1 Hz, 1H, H8), 3.70 (dd, 3J = 8.7 Hz,
3J = 6.5 Hz, 1H, H9), 4.02 (d, 2J = 15.3 Hz, 1H, Ph-
CH2), 4.35 (s, 1H, H4), 4.62 (d, 4J = 2.1 Hz, 1H, H6), 4.98
(d, 2J = 15.3 Hz, 1H, Ph-CH2), 7.20–7.38 (m, 5H, Ph)
ppm; 13C NMR: d = 23.8 (C8), 24.0 (CH3), 27.5 (CH3),
28.4 (CH), 35.9 (C9-C), 37.3 (CH2), 38.6 (CH2), 48.1 (Ph-
CH2), 54.2 (C5), 72.8 (C9), 84.3 (C4), 109.1 (C6), 127.9
(CH), 128.6 (2 9 CH), 129.0 (2 9 CH), 136.1 (C, Ph),
150.6 (C7), 165.4 (C2) ppm; IR: ꢀm = 2,964, 2,947, 2,857,
1,716 (C=O), 1,496, 1,455, 1,405, 1,362, 1,280, 1,252,
1,200, 1,180, 1,158, 1,119, 1,026 cm-1; MS: m/z (%) =
403 (M?, 96), 388 (21), 285 (69), 135 (84), 108 (16), 91
(100), 79 (30), 67 (15).
ꢀ
140.3 (C, Ph), 147.1 (C7), 189.1 (C2) ppm; IR: m = 3,017,
2,969, 2,905, 2,851, 2,810, 1,712, 1,598, 1,498, 1,455,
1,405, 1,333, 1,257, 1,218, 1,114, 1,046 cm-1; MS:
m/z (%) = 504 (M?, 19), 369 (40), 283 (44), 234 (82),
147 (100), 135 (32); HRMS: m/z calcd. for C30H41N4OS?
505.2996, found 505.3008; CCDC number 875881.
(4R*,9R*)-6,9-Di-(1-adamantyl)-5,5-dimethyl-3-phenyl-
1,3,10-triazatricyclo[5.2.1.04,10]dec-6-ene-2-thione
(6j, C35H45N3S)
Yield 14 % (4 h); m.p.: 211.0–212.0 °C; 1H NMR:
d = 0.92 (s, 3H, CH3), 1.37 (s, 3H, CH3), 1.53–2.18 (m,
30H, 2 9 Ad), 2.60–2.85 (m, 2H, H8), 4.23–4.35 (m, 1H,
H9), 5.01 (s, 1H, H4), 7.20–7.50 (m, 5H, Ph) ppm; 13C
NMR: d = 24.7 (CH3), 26.1 (C8), 28.5 (CH), 28.9 (CH),
29.8 (CH3), 35.8 (C9-C), 36.1 (C6-C), 37.0 (CH2), 37.3
(CH2), 39.0 (CH2), 42.6 (CH2), 57.4 (C5), 75.3 (C9), 91.6
(C4), 126.2 (C6), 127.8 (CH), 127.9 (2 9 CH), 129.1
(2 9 CH), 141.0 (C, Ph), 142.7 (C7), 190.2 (C2) ppm; IR:
(4R*,9R*)-9-(1-Adamantyl)-3-benzyl-5,5-dimethyl-1,3,10-
triazatricyclo[5.2.1.04,10]dec-6-ene-2-thione
(6m, C26H33N3S)
Yield 25 % (5 h); m.p.: 197.0–200.5 °C; 1H NMR:
d = 1.20 (s, 3H, CH3), 1.26 (s, 3H, CH3), 1.60–1.74 (m,
12H, Ad), 2.00–2.05 (m, 3H, Ad), 2.40 (dd, J = 15.5 Hz,
2
ꢀ
m = 2,957, 2,920, 2,888, 2,847, 1,598, 1,499, 1,453, 1,408,
3J = 8.8 Hz, 1H, H8), 2.56 (ddd, 2J = 15.5 Hz, 3J =
1,387, 1,293, 1,275, 1,226 cm-1; MS: m/z (%) = 539 (M?,
7), 404 (43), 269 (100), 135 (88).
4
2
5.5 Hz, J = 2.3 Hz, 1H, H8), 4.25 (d, J = 15.3 Hz, 1H,
Ph-CH2), 4.34 (dd, 3J = 8.8 Hz, 3J = 5.5 Hz, 1H, H9),
4
(4R*,9R*)-9-(1-Adamantyl)-5,5,9-trimethyl-6-
(morpholinomethyl)-3-phenyl-1,3,10-triazatricyclo-
[5.2.1.04,10]dec-6-en-2-one (6k, C31H42N4O2)
Yield 28 % (4 h); m.p.: 206.0–208.0 °C; 1H NMR:
d = 0.87 (s, 3H, CH3), 1.38 (s, 3H, CH3), 1.50 (s, 3H,
CH3), 1.61–1.76 (m, 12H, Ad), 2.01–2.06 (m, 3H, Ad),
2.14 (d, 2J = 14.3 Hz, 1H, H8), 2.23–2.50 (m, 4H,
N-CH2), 2.80 (d, 2J = 13.0 Hz, 1H, C6-CH2), 2.87 (d,
4.45 (s, 1H, H4), 4.62 (d, J = 2.3 Hz, 1H, H6), 5.84 (d,
2J = 15.3 Hz, 1H, Ph-CH2), 7.27–7.38 (m, 5H, Ph) ppm;
13C NMR: d = 23.8 (C8), 24.2 (CH3), 28.1 (CH3), 28.4
(CH), 36.3 (C9-C), 37.2 (CH2), 39.0 (CH2), 51.3 (Ph-CH2),
55.5 (C5), 75.2 (C9), 87.3 (C4), 108.9 (C6), 128.1 (CH),
128.5 (2 9 CH), 129.1 (2 9 CH), 135.3 (C, Ph), 149.5
(C7), 189.1 (C2) ppm; IR: ꢀm = 3,018, 2,963, 2,906, 2,850,
1,681, 1,604, 1,495, 1,448, 1,423, 1,314, 1,216, 1,150,
123

216
J. Galeta et al.
1,050 cm-1; MS: m/z (%) = 419 (M?, 55), 271 (18), 135
(100), 106 (21), 91 (90), 79 (26); CCDC number 875430.
Acknowledgments The research was supported by the Grant
Agency of the Czech Republic, grant no. 203/09/1345. We are
ˇ
grateful to Marek Necas for crystallographic measurements and to
Lukas Maier for NMR measurements on the Bruker Avance 500.
´ˇ
(4R*,9R*)-9-(1-Adamantyl)-3-benzyl-5,5,6-trimethyl-
1,3,10-triazatricyclo[5.2.1.04,10]dec-6-en-2-one
(6n, C27H35N3O)
References
Yield 53 % (2.5 h); m.p.: 168.0–169.0 °C; 1H NMR:
d = 1.09 (s, 3H, CH3), 1.13 (s, 3H, CH3), 1.49 (d,
5J = 1.6 Hz, 3H, C6-CH3), 1.52–1.58 (m, 3H, Ad), 1.62–
1.74 (m, 9H, Ad), 1.99–2.03 (m, 3H, Ad), 2.32 (dd,
2J = 14.9 Hz, 3J = 8.6 Hz, 1H, H8), 2.39 (ddm, 2J =
14.9 Hz, 3J = 6.5 Hz, 1H, H8), 3.65 (dd, 3J = 8.6 Hz,
3J = 6.5 Hz, 1H, H9), 3.99 (d, 2J = 15.3 Hz, 1H,
Ph-CH2), 4.36 (s, 1H, H4), 4.98 (d, 2J = 15.3 Hz, 1H,
Ph-CH2), 7.21–7.37 (m, 5H, Ph) ppm; 13C NMR: d = 8.5
(C6-CH3), 21.8 (CH3), 22.5 (C8), 25.6 (CH3), 28.4 (CH),
35.9 (C9-C), 37.3 (CH2), 38.7 (CH2), 48.2 (Ph-CH2), 54.7
(C5), 72.3 (C9), 83.8 (C4), 115.0 (C6), 127.9 (CH), 128.6
(2 9 CH), 129.0 (2 9 CH), 136.2 (C, Ph), 144.0 (C7),
ˇ
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165.8 (C2) ppm; IR: m = 3,065, 3,016, 2,961, 2,905, 2,850,
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1,694 (C=O), 1,446, 1,409, 1,361, 1,248, 1,216, 1,121,
1,012 cm-1; MS: m/z (%) = 417 (M?, 100), 322 (47), 299
(23), 149 (17), 135 (34), 91 (41), 69 (18); HRMS: m/z
calcd. for C27H36N3O? 418.2853, found 418.2859.
67:40
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(4R*,9R*)-9-(1-Adamantyl)-3-benzyl-5,5,6-trimethyl-
1,3,10-triazatricyclo[5.2.1.04,10]dec-6-ene-2-thione
(6o, C27H35N3S)
Yield 10 % (2.5 h); m.p.: 163.0–164.0 °C; 1H NMR:
d = 1.12 (s, 3H, CH3), 1.19 (s, 3H, CH3), 1.48 (d,
5J = 1.5 Hz, 3H, C6-CH3), 1.61–1.74 (m, 12H, Ad),
2.00–2.05 (m, 3H, Ad), 2.37 (dd, 2J = 15.1 Hz,
3J = 8.8 Hz, 1H, H8), 2.47 (ddm, 2J = 15.1 Hz,
3J = 5.5 Hz, 1H, H8), 4.23 (d, 2J = 15.3 Hz, 1H, Ph-
´
3
3
CH2), 4.29 (dd, J = 8.8 Hz, J = 5.5 Hz, 1H, H9), 4.46
2
(s, 1H, H4), 5.84 (d, J = 15.3 Hz, 1H, Ph-CH2), 7.26–
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7.41 (m, 5H, Ph) ppm; 13C NMR: d = 8.2 (C6-CH3), 21.9
(CH3), 22.6 (C8), 26.3 (CH3), 28.4 (CH), 36.3 (C9-C), 37.2
(CH2), 39.0 (CH2), 51.4 (Ph-CH2), 55.8 (C5), 74.7 (C9),
86.9 (C4), 114.7 (C6), 128.1 (CH), 128.5 (2 9 CH), 129.0
(2 9 CH), 135.4 (C, Ph), 143.0 (C7), 189.3 (C2) ppm; IR:
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(53), 122 (19), 107 (18), 91 (100), 79 (30), 67 (15); HRMS:
m/z calcd. for C27H36N3S? 434.2624, found 434.2631;
CCDC number 875431.
123