Synthesis of new tricyclic spirobispidines via ring closing metathesis reaction

Article abstract of DOI:10.3987/COM-07-11063

New tricyclic spiro compounds based on 3,7-diazabicyclo[3.3.1]- nonane (bispidine) wcre synthesized by ruthenium-catalyzed ring closing metathesis reactions. The constitution of the newly formed double bond depending on the chain length and various conditions of the RCM reaction was analyzed.

Full text of DOI:10.3987/COM-07-11063

HETEROCYCLES, Vol. 71, No. 11, 2007
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HETEROCYCLES, Vol. 71, No. 11, 2007, pp. 2331 - 2345. © The Japan Institute of Heterocyclic Chemistry
Received, 26th March, 2007, Accepted, 25th July, 2007, Published online, 3rd August, 2007. COM-07-11063
SYNTHESIS OF NEW TRICYCLIC SPIROBISPIDINES VIA RING
CLOSING METATHESIS REACTION
Christian Hametner,*,a Daniel Dangl,a Kurt Mereiter,b Martina Marchetti,b
and Johannes Fröhlicha
a Vienna University of Technology, Institute of Applied Synthetic Chemistry,
Getreidemarkt 9/163, 1060 Vienna, Austria
E-mail: christian.hametner@tuwien.ac.at
b Vienna University of Technology, Institute of Chemical Technologies and
Analytics, Getreidemarkt 9/164, 1060 Vienna, Austria
Abstract – New tricyclic spiro compounds based on 3,7-diazabicyclo[3.3.1]-
nonane (bispidine) were synthesized by ruthenium-catalyzed ring closing
metathesis reactions. The constitution of the newly formed double bond
depending on the chain length and various conditions of the RCM reaction was
analyzed.
INTRODUCTION
The development of new nitrogen-containing ligands for organic synthesis is of continuous interest. In
particular for metal-catalyzed reactions, ligands derived from amino acids or alkaloids recently gained
increasing importance.1
The tetracyclic alkaloid sparteine was introduced as an efficient ligand e.g. for Pd-catalyzed allylation
reactions2 or the addition of organolithium compounds to imines.3 3,7-Diazabicyclo[3.3.1]nonane
(bispidine) constitutes the B and C rings of sparteine as well as many other lupanine alkaloids (Scheme 1).
Some stable bispidine-metal complexes have been described in the literature, for instance with NiII, CuII,4
or Ni0,5 and applications of bispidine ligands in transformations of organozinc compounds have been
given.6

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HETEROCYCLES, Vol. 71, No. 11, 2007
6
5
N7
N
4
9
8
3 N
N
1
2
bispidine
sparteine
Scheme 1
Depending on the desired substitution pattern, several synthetic approaches towards bispidine derivatives
are possible: a double Mannich reaction of piperidones with appropriate primary amines yields
bispidinones,7 a sequence starting from pyridine derivatives via hydrogenation leads to miscellaneous
bispidine derivatives.4 A third method describes the synthesis of 9,9-dialkyl-2,4,6,8-tetraoxobispidines by
a Guareschi reaction8,9 from a ketone, which may be cyclic to generate a spiro center at position 9.
We chose the latter as starting point for the construction of novel tricyclic spirobispidines of potential
interest as precursors for new ligands. An additional bridge connecting the two nitrogen atoms should
constitute the third ring and a ring closing metathesis (RCM) reaction10 seemed a promising approach for
its realization, leading to ring systems not previously described in the literature. Herein we present the
synthesis of the metathesis precursors and results of RCM reactions under varying conditions, including
the analysis of the configuration of the newly formed double bond.
RESULTS AND DISCUSSION
The N-unsubstituted spirotetraoxobispidines 1 and 2 were synthesized from cyclopentanone and
cyclohexanone by a Guareschi reaction followed by acidic hydrolysis.9 N,N’-Disubstitution was also
performed in accordance to the literature,9 introducing ω-alkenyl chains from propenyl to hexenyl
(Scheme 2).
( )n
( )n
NC
NC
O
O
O
O
O
O
( )n
a.
c.
b.
NH
O
N
O
O
( )m
N
N
( )n
O
H
N
( )m
O
H
1,2
3 - 10
Scheme 2. Synthesis of dialkenyl spirobispidines (n=1-2, m=1-4): (a.) ethyl cyanoacetate,
NH3, dry EtOH, 49-65%; (b.) 60% H2SO4, 67-73%; (c.) K2CO3, bromoalkene, 29-71%

HETEROCYCLES, Vol. 71, No. 11, 2007
2333
Three series of RCM reactions were carried out with these precursors (Scheme 3). Two of these were run
under conventional heating, one using the more common 1st generation Grubbs catalyst, the other its 2nd
generation analogue (Scheme 4), which tolerates a larger bandwidth of substrates, produces better yields,
and shows more stability towards elevated temperatures, and the final one used microwave heating, where
only the 2nd generation Grubbs is applicable.11
( )n
( )n
O
O
O
O
N
N
O
O
( )m
( )m
O
O
N
N
( )m
( )m
5 - 10
11 - 16
Scheme 3. General scheme of the ring closing metathesis reaction (n=1-2, m=2-4)
PCy3
Ru
N Mes
Ph
Mes N
Cl
Ph
Cl
Cl
Ru
Cl
PCy3
PCy3
Scheme 4. RCM catalysts: Grubbs catalyst 1st (left) and 2nd (right) generation
(Cy = cyclohexyl, Mes = mesityl)
In the first series the precursors were subjected to metathesis reactions in dry degassed CH2Cl2 under reflux
overnight using 10 mol% of 1st generation Grubbs catalyst (Table 1). No ring closure at all was observed
starting from the dipropenyl compounds, neither here nor in any other of the following experiments.
Apparently the distance between the nitrogen atoms of tetraoxobispidines is too short to be bridged via a
2-butenyl chain. All other experiments resulted in acceptable yields of ring-closed products, and the size of
the spiro ring had no influence on the course of the reaction. Unexpected results were found for the
configuration of the newly formed double bond: from the dibutenyl substrates 5 and 6 E-configured
products 11 and 12 were formed exclusively, whereas dipentenyl precursors 7 and 8 selectively yielded 13a
and 14a with opposite configuration. The configuration of the double bond was established by X-ray
crystallography (as an example the structure of compound 13a is shown in Figure 1). Only in the case of the
dihexenyl starting compounds 9 and 10 mixtures of stereoisomers were obtained (the configuration and
ratios given in the tables were determined by analysis of the olefinic signals in the 1H-NMR spectra).

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HETEROCYCLES, Vol. 71, No. 11, 2007
Substrate
m
1
1
2
2
3
3
4
4
n
1
2
1
2
1
2
1
2
Product
Yield
-
Double bond configuration
3
4
-
-
-
5
11
12
13a
14a
15
16
53%
48%
60%
69%
51%
60%
E
6
E
7
Z
8
Z
9
Z/E= 2.6:1
Z/E= 1.4:1
10
Table 1. Grubbs catalyst 1st generation, thermal heating (CH2Cl2, reflux, 15 h)
Analogous reactions were then carried out for all substrates with the use of 2nd generation Grubbs catalyst
(Table 2), resulting in slightly better yields in most cases. While product composition was similar for the
other chains, the opposite stereochemistry was observed in case of the dipentenyl compounds (Figure 2
shows the X-ray crystal structure of 13b). Such a complete inversion of selectivity is unprecedented in the
literature for these two catalysts.
Substrate
m
1
1
2
2
3
3
4
4
n
1
2
1
2
1
2
1
2
Product
Yield
-
Double bond configuration
3
4
-
-
-
5
11
12
13b
14b
15
16
80%
65%
79%
59%
36%
66%
E
6
E
7
E
8
E
9
Z/E= 1.9:1
Z/E= 1.5:1
10
Table 2. Grubbs catalyst 2nd generation, thermal heating (CH2Cl2, reflux, 15 h)
In the literature several applications of microwave heating in RCM chemistry are described with good
yields and excellent substrate acceptance using 2nd generation Grubbs catalyst .11,12 Thus another series of
experiments was carried out (Table 3), where the reaction mixtures were heated by microwave irradiation
(125 °C, 7 min) instead of refluxing overnight, mainly in order to investigate the influence of these differing
conditions on the double bond configuration. Substantial difference to the conventional method was only

HETEROCYCLES, Vol. 71, No. 11, 2007
2335
observed for the middle-sized substrates 7 and 8, where the stereoselectivity was lost and isomeric
mixtures were produced, as it was again the case for the large rings 15 and 16. With the dibutenyl
precursors however selectivity and good yields were preserved, so the syntheses of 11 and 12 can benefit
from the typical short reaction times of this technique.
Substrate
m
1
1
2
2
3
3
4
4
n
1
2
1
2
1
2
1
2
Product
Yield
-
Double bond configuration
3
4
-
-
11
-
5
72%
66%
74%
65%
68%
63%
E
6
12
E
7
13a/13b
14a/14b
15
Z/E= 1:1.5
Z/E= 1:1.5
Z/E= 2.4:1
Z/E= 1.7:1
8
9
10
16
Table 3. Grubbs catalyst 2nd generation, microwave irradiation (CH2Cl2, 125 °C, 7 min)
Figure 1. ORTEP view of the molecular
Figure 2. ORTEP view of the molecular
structure of 13a in crystalline state.
structure of 13b in crystalline state.

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HETEROCYCLES, Vol. 71, No. 11, 2007
Finally the tricyclic parent systems should be approached by subjecting the metathesis products 11-16 to
a two-step reduction sequence. The hydrogenation was performed in a Parr apparatus at 60 psi using 10%
Pd/C as catalyst (Scheme 5) and worked well for the thirteen-membered (conversion of both isomers of
13 and 14 to 17 and 18) as well as the fifteen-membered ring systems (syntheses of 19 and 20 from the
isomeric mixtures 15 and 16). However, the reaction failed for the smallest rings 11 and 12, and an
alternative attempt under homogeneous conditions using tris(triphenylphosphine)rhodium(I) chloride13
(Wilkinson's catalyst) was unsuccessful as well.
The final reduction of the imido groups was carried out only with the hydrogenated products 17-20 by
using sodium bis(2-methoxyethoxy)aluminium hydride solution (Red-Al®) in toluene to obtain amines
21-24, which turned out to be quite unstable.
( )n
( )n
( )n
O
O
O
O
b.
a.
N
N
N
( )m
( )m
O
O
O
O
( )m
N
( )m
N
( )m
N
( )m
13 - 16
17 - 20
21 - 24
Scheme 5. Hydrogenation and subsequent reduction of the metathesis products (n=1-2, m=3-4):
(a.) 10% Pd/C, ethanol/dioxane, H2, 60 psi, 93-98%; (b.) Red-Al®, toluene, 68-81%
In conclusion, we synthesized a series of new tricyclic ring systems based on 3,7-diazabicyclo[3.3.1]-
nonane (bispidine) by ring closing metathesis reactions. The size of the new-formed rings ranges from 11
to 15, a nine-membered analogue could not be obtained. The configuration of the resulting double bond
was found to be influenced not only by the size of the formed ring, but also by experimental parameters
like the nature of the catalyst and the heating method. Some of the metathesis products were reduced to
the tricyclic parent compounds. Various other applications of RCM chemistry on spirotetraoxobispidines
are currently underway in our laboratory.
EXPERIMENTAL
General. Unless otherwise noted, chemicals were purchased from commercial suppliers and used without
further purification. All solvents were distilled prior to use. Dry dimethylformamide (DMF; from Acros)
and dry ethanol (from Merck) were used as received, dry dichloromethane (CH2Cl2) was obtained by

HETEROCYCLES, Vol. 71, No. 11, 2007
2337
refluxing over P2O5, dry toluene by refluxing over sodium. Flash column chromatography was performed
on silica gel 60 from Merck (40 – 63 µm) by eluting with mixtures of light petroleum (boiling range 40 –
60°C) and ethyl acetate (EtOAc) of varying compositions. Microwave reactions were carried out on a
CEM Explorer PLSTM microwave unit. Melting points were determined using a Kofler-type Leica Galen
III micro-hot-stage microscope and are uncorrected. Elemental analyses were carried out in the
Microanalytical Laboratory, University of Vienna. NMR spectra were recorded from solutions in CDCl3
on a Bruker DPX-200 (200 MHz) spectrometer and chemical shifts are reported in ppm using Me4Si as
internal standard. MALDI-TOF spectra were obtained with a Shimadzu AXIMA LNR spectrometer using
5-chloro-2-mercaptobenzothiazole and 1,3-dihydroxynaphthaline as the matrices. Tetraoxo compounds 1
9
and 2 as starting materials were synthesized following a previously described method.
General Procedure for Dialkylated Tetraoxo Compounds 3-10. A solution of tetraoxo compound 1 or
2 (1.0 equiv.) in dry DMF (10% solution) was heated to a temperature of 60 °C to 70 °C. Then NaH (2.5
equiv.) was added, and the mixture was heated to reflux for about 1h. After cooling a solution of the freshly
distilled bromoalkene (3.0 equiv) in dry DMF (50% solution) was added. The resulting mixture was
refluxed for 90 min. Thereafter most of the solvent was distilled off under reduced pressure. CH2Cl2 was
added to the residue and the mixture was washed with water. The aqueous phase was extracted with CH2Cl2
twice. The combined organic layers were washed with water for three times and dried over Na2SO4. After
distilling off the solvent, the residue was either recrystallized or purified by flash column chromatography.
3’,7’-Diprop-2-enylspiro[cyclopentane-1,9’-[3,7]-diazabicyclo[3.3.1]nonane]-2’,4’,6’,8’-tetraone (3).
Tetraoxo compound 1 (3.0 g, 13 mmol) was reacted with allyl bromide (4.6 g, 38 mmol) to give 3 (1.9 g,
47%). Recrystallized from EtOAc, Mp 124-127 °C, TLC: Rf= 0.27 (light petroleum/EtOAc, 5:1),
1H-NMR (200 MHz, CDCl3): δ = 5.83 – 5.59 (m, 2 H), 5.25 – 5.07 (m, 4 H), 4.33 (d, J = 6.0 Hz, 4 H),
3.81 (s, 2 H), 1.87 – 1.49 (m, 10 H) ppm. 13C-NMR (50 MHz, CDCl3): δ = 164.8 (s, 4 C), 130.4 (d, 2 C),
119.2 (t, 2 C), 59.3 (d, 2 C), 43.0 (s, 1 C), 42.3 (t, 2 C), 35.2 (t, 2 C), 24.5 (t, 2 C) ppm. Anal. Calcd for
C17H20N2O4 (316.36): C 64.54 H 6.37 N 8.85. Found: C 64.44 H 6.39 N 8.68.
3’,7’-Diprop-2-enylspiro[cyclohexane-1,9’-[3,7]-diazabicyclo[3.3.1]nonane]-2’,4’,6’,8’-tetraone (4).
Tetraoxo compound 2 (2.0 g, 8 mmol) was reacted with allyl bromide (2.9 g, 24 mmol) to give 4 (0.9 g,
34%). Purified by chromatography (light petroleum/EtOAc, 5:1), Mp 106-108 °C, TLC: Rf= 0.35 (light
petroleum/EtOAc, 5:1), 1H-NMR (200 MHz, CDCl3): δ = 5.82 – 5.58 (m, 2 H), 5.27 – 5.07 (m, 4 H), 4.32 (d,
J = 5.2 Hz, 4 H), 3.91 (s, 2 H), 1.63 – 1.39 (s, 10 H) ppm. 13C-NMR (50 MHz, CDCl3): δ = 164.6 (s, 4 C),

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HETEROCYCLES, Vol. 71, No. 11, 2007
130.3 (d, 2 C), 119.6 (t, 2 C), 58.3 (d, 2 C), 42.2 (t, 2 C), 36.2 (s, 1 C), 32.4 (t, 2 C), 25.0 (t, 1 C), 20.7 (t,
2 C) ppm. Anal. Calcd for C17H20N2O4 (316.36): C 64.54 H 6.37 N 8.85. Found: C 64.44 H 6.39 N 8.68.
3’,7’-Dibut-3-enylspiro[cyclopentane-1,9’-[3,7]-diazabicyclo[3.3.1]nonane]-2’,4’,6’,8’-tetraone (5).
Tetraoxo compound 1 (3.0 g, 13 mmol) was reacted with 4-bromo-1-butene (5.1 g, 38 mmol) to give 5 (1.4
g, 29%). Purified by chromatography (light petroleum/EtOAc, 4:1), Mp 84-87 °C, TLC: Rf = 0.44 (light
petroleum/EtOAc, 4:1), 1H-NMR (200 MHz, CDCl3): δ = 5.82 – 5.56 (m, 2 H), 5.04 – 4.86 (m, 4 H), 3.84 (t,
J = 6.9 Hz, 4 H), 3.76 (s, 2 H), 2.37 – 2.22 (m, 4 H), 1.80 – 1.52 (m, 8 H) ppm. 13C-NMR (50 MHz, CDCl3):
δ = 165.3 (s, 4 C), 134.4 (d, 2 C), 117.5 (t, 2 C), 59.5 (d, 2 C), 42.9 (s, 1 C), 39.3 (t, 2 C), 35.4 (t, 2 C),
32.1 (t, 2 C), 24.6 (t, 2 C) ppm. Anal. Calcd for C19H24N2O4 (344.41): C 66.26 H 7.02 N 8.13. Found: C
66.48 H 7.33 N 7.95.
3’,7’-Dibut-3-enylspiro[cyclohexane-1,9’-[3,7]-diazabicyclo[3.3.1]nonane]-2’,4’,6’,8’-tetraone
(6).
Tetraoxo compound 2 (5.0 g, 20 mmol) was reacted with 4-bromo-1-butene (8.1 g, 60 mmol) to give 6
(5.1 g, 71%). Recrystallized from EtOAc, Mp 110-111 °C, TLC: Rf = 0.53 (light petroleum/EtOAc, 7:1),
1H-NMR (200 MHZ, CDCl3): δ = 5.79 – 5.52 (m, 2 H), 4.99 – 4.82 (m, 4 H), 3.86 (s, 2 H), 3.79 (t, J= 6.9
Hz, 4 H), 2.37 – 2.18 (m, 4 H), 1.60 – 1.39 (m, 10 H) ppm. 13C-NMR (50 MHz, CDCl3): δ = 165.0 (s, 4
C), 134.5 (d, 2 C), 117.4 (t, 2 C), 58.4 (d, 2 C), 39.3 (t, 2 C), 36.1 (s, 1 C), 32.5 (t, 2 C), 32.0 (t, 2 C), 25.1
(t, 1 C), 20.7 (t, 2 C) ppm. Anal. Calcd for C20H26N2O4 (358.44): C 67.02, H 7.31, N 7.82. Found: C
66.72 H 7.60 N 7.98.
3’,7’-Dipent-4-enylspiro[cyclopentane-1,9’-[3,7]-diazabicyclo[3.3.1]nonane]-2’,4’,6’,8’-tetraone (7).
Tetraoxo compound 1 (3.0 g, 13 mmol) was reacted with 5-bromo-1-pentene (5.7 g, 38 mmol) to give 7
(2.7 g, 57%). Purified by chromatography (light petroleum/EtOAc, 6:1), Mp 49-51 °C, TLC: Rf = 0.27
1
(light petroleum/EtOAc, 6:1), H-NMR (200 MHz, CDCl3): δ = 5.84 – 5.58 (m, 2 H), 5.06 – 4.83 (m, 4
H), 3.76 (s, 2 H) 3.71 (t, J = 7.6 Hz, 4 H), 2.08 – 1.86 (m, 4 H), 1.83 – 1.40 (m, 12 H) ppm. 13C-NMR (50
MHz, CDCl3): δ = 165.1 (s, 4 C), 136.9 (d, 2 C), 115.3 (t, 2 C), 59.4 (d, 2 C), 42.8 (s, 1 C), 39.9 (t, 2 C),
35.1 (t, 2 C), 30.7 (t, 2 C), 26.5 (t, 2 C), 24.5 (t, 2 C) ppm. Anal. Calcd for C21H28N2O4 (372.47): C 67.72
H 7.58 N 7.52. Found: C 67.68 H 7.81 N 7.40.
3’,7’-Dipent-4-enylspiro[cyclohexane-1,9’-[3,7]-diazabicyclo[3.3.1]nonane]-2’,4’,6’,8’-tetraone (8).
Tetraoxo compound 2 (4.2 g, 17 mmol) was reacted with 5-bromo-1-pentene (7.5 g, 50 mmol) to give 8 (4.5
g, 70%). Purified by chromatography (light petroleum/EtOAc, 7:1), Mp 41-43 °C, TLC: Rf = 0.24 (light
petroleum/EtOAc, 7:1), 1H-NMR (200 MHz, CDCl3): δ = 5.83 – 5.57 (m, 2 H), 5.07 – 4.83 (m, 4 H), 3.88 (s,

HETEROCYCLES, Vol. 71, No. 11, 2007
2339
13
2 H), 3.71 (t, J = 7.5 Hz, 4 H), 2.10 – 2.86 (m, 4 H), 1.63 – 1.39 (m, 14 H) ppm. C-NMR (50 MHz,
CDCl3): δ = 164.9 (s, 4 C), 136.9 (d, 2 C), 115.3 (t, 2 C), 58.4 (d, 2 C), 39.9 (t, 2 C), 36.0 (s, 1 C), 32.4 (t,
2 C), 30.8 (t, 2 C), 26.4 (t, 2 C), 25.1 (t, 1 C), 20.7 (t, 2 C) ppm. Anal. Calcd for C22H30N2O4 (386.50): C
68.37 H 7.82 N 7.25. Found: C 68.64 H 7.96 N 7.30.
3’,7’-Dihex-5-enylspiro[cyclopentane-1,9’-[3,7]-diazabicyclo[3.3.1]nonane]-2’,4’,6’,8’-tetraone (9).
Tetraoxo compound 1 (2.4 g, 10 mmol) was reacted with 6-bromo-1-hexene (5.0 g, 30 mmol) to give 9
(1.6 g, 39%). Purified by chromatography (light petroleum/EtOAc, 6:1), Mp 32-34 °C, TLC: Rf = 0.55
1
(light petroleum/EtOAc, 4:1), H-NMR (200 MHz, CDCl3): δ = 5.86 – 5.58 (m, 2 H), 5.03 – 4.82 (m, 4
H), 3.80 – 3.63 (m, 6 H), 2.10 – 1.89 (m, 4 H), 1.79 – 1.21 (m, 16 H) ppm. 13C-NMR (50 MHz, CDCl3): δ
= 165.2 (s, 4 C), 137.9 (d, 2 C), 114.9 (t, 2 C), 59.5 (d, 2 C), 42.8 (s, 1 C), 40.2 (t, 2 C), 35.2 (t, 2 C), 33.0
(t, 2 C), 26.8 (t, 2 C), 25.9 (t, 2 C), 24.5(t, 2 C) ppm. Anal. Calcd for C23H32N2O4 (400.52): C 68.97 H
8.05 N 6.99. Found: C 69.10 H 8.25 N 7.02.
3’,7’-Dihex-5-enylspiro[cyclohexane-1,9’-[3,7]-diazabicyclo[3.3.1]nonane]-2’,4’,6’,8’-tetraone (10).
Tetraoxo compound 2 (1.8 g, 7.2 mmol) was reacted with 6-bromo-1-hexene (3.5 g, 21.6 mmol) to give
10 (1.9 g, 63%). Purified by chromatograph (light petroleum/EtOAc, 7:1), colourless oil, TLC: Rf = 0.45
1
(light petroleum/EtOAc, 7:1), H-NMR (200 MHz, CDCl3): δ = 5.84 – 5.58 (m, 2 H), 5.05 – 4.84 (m, 4
H), 3.87 (s, 2 H), 3.71 (t, J = 7.6 Hz, 4 H), 2.10 – 1.91 (m, 4 H), 1.63 – 1.17 (m, 18 H) ppm. 13C-NMR (50
MHz, CDCl3): δ = 165.0 (s, 4 C), 137.9 (d, 2 C), 114.8 (t, 2 C), 58.5 (d, 2 C), 40.1 (t, 2 C), 36.0 (s, 1 C),
33.0 (t, 2 C), 32.5 (t, 2 C), 26.8 (t, 2 C), 25.9 (t, 2 C), 25.1 (t, 1 C), 20.7 (t, 2 C) ppm. Anal. Calcd for
C24H34N2O4 (414.55): C 69.54 H 8.27 N 6.76. Found: C 69.31 H 8.01 N 7.06.
General Procedure for Ring Closing Metathesis Products 11-16 under Thermal Heating. To a
solution of the diolefine 5-10 (1.0 equiv.) in dry degassed CH2Cl2 (0.1% solution) were added either
Grubbs catalyst 1st or 2nd generation (10 mol%) and the resulting mixture was refluxed for 15 h under an
argon atmosphere. Thereafter the solvent was distilled off and the product purified by flash column
chromatography (light petroleum/EtOAc, 4:1).
E-Spiro[cyclopentane-1,13’-[3,10]-diazatricyclo[8.3.1.13,12]-6-pentadecene]-2’,11’,14’,15’-tetraone
(11). Diolefine 5 (500 mg, 1.54 mmol) was converted using Grubbs catalyst 2nd generation (120 mg, 10
mol%) to give 11 (370 mg, 80%) as colorless crystals. Mp 252-254 °C, TLC: Rf = 0.26 (light
petroleum/EtOAc, 4:1), 1H-NMR (200 MHz, CDCl3): δ = 5.03 – 4.77 (m, 2 H), 4.32 – 4.07 (m, 2 H), 3.78
– 3.56 (m, 4 H), 2.50 – 2.00 (m, 4 H), 1.80 – 1.44 (m, 8 H) ppm. 13C-NMR (50 MHz, CDCl3): δ = 166.0 (s, 2

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HETEROCYCLES, Vol. 71, No. 11, 2007
C), 165.1 (s, 2 C), 129.8 (d, 2 C), 60.2 (d, 2 C), 42.0 (s, 1 C), 38.1 (t, 2 C), 35.6 (t, 2 C), 29.5 (t, 2 C), 24.4
(t, 2 C) ppm. Anal. Calcd for C17H20N2O4 (316.36): C 64.54 H 6.37 N 8.85. Found: C 64.71 H 6.59 N
8.67.
E-Spiro[cyclohexane-1,13’-[3,10]-diazatricyclo[8.3.1.13,12]-6-pentadecene]-2’,11’,14’,15’-tetraone
(12). Diolefine 6 (200 mg, 0.56 mmol) was converted using Grubbs catalyst 2nd generation (50 mg, 10
mol%) to give 12 (120 mg, 65%) as colorless crystals. Mp 243-244 °C, TLC: Rf = 0.36 (light
petroleum/EtOAc, 4:1), 1H-NMR (200 MHz, CDCl3): δ = 5.04 – 4.81 (m, 2 H), 4.31 – 4.08 (m, 2 H), 3.84
13
(s, 2 H), 3.75 – 3.57 (m, 2 H), 2.50 – 2.05 (m, 4 H), 1.57 – 1.29 (m, 10 H) ppm. C-NMR (50 MHz,
CDCl3): δ = 165.9 (s, 2 C), 164.9 (s, 2 C), 130.0 (d, 2 C), 59.6 (d, 2 C), 38.0 (t, 2 C), 35.4 (s, 1 C), 33.1 (t,
2 C), 29.7 (t, 2 C), 25.1 (t, 1 C), 20.7 (t, 2 C) ppm. Anal. Calcd for C18H22N2O4 (330.39): C 65.44 H 6.71
N 8.48. Found: C 65.15 H 6.99 N 8.37.
Z-Spiro[cyclopentane-1,15’-[3,12]-diazatricyclo[10.3.1.13,14]-7-heptadecene]-2’,13’,16’,17’-tetraone
(13a). Diolefine 7 (500 mg, 1.34 mmol) was converted using Grubbs catalyst 1st generation (110 mg, 10
mol%) to give 13a (270 mg, 60%) as colorless crystals. Mp 224-226 °C, TLC: Rf = 0.32 (light
petroleum/EtOAc, 4:1), 1H-NMR (200 MHz, CDCl3): δ = 5.54 – 5.32 (m, 2 H), 3.99 – 3.85 (m, 4 H), 3.83
(s, 2 H), 1.87 – 1.42 (m, 16 H) ppm. 13C-NMR (50 MHz, CDCl3): δ = 166.0 (s, 4 C), 129.1 (d, 2 C), 60.2
(d, 2 C), 43.1 (s, 1 C), 39.3 (t, 2 C), 35.4 (t, 2 C), 28.2 (t, 2 C), 24.5 (t, 2 C), 23.3 (t, 2 C) ppm. Anal.
Calcd for C19H24N2O4 (344.41): C 66.26 H 7.02 N 8.13. Found: C 66.29 H 7.21 N 8.08.
E-Spiro[cyclopentane-1,15’-[3,12]-diazatricyclo[10.3.1.13,14]-7-heptadecene]-2’,13’,16’,17’-tetraone
(13b). Diolefine 7 (500 mg, 1.34 mmol) was converted using Grubbs catalyst 2nd generation (120 mg, 10
mol%) to give 13b (370 mg, 80%) as colorless crystals. Mp 252-254 °C, TLC: Rf = 0.32 (light
1
petroleum/EtOAc, 4:1), H-NMR (200 MHz, CDCl3): δ = δ 5.24 – 4.97 (m, 2 H), 3.94 – 3.78 (m, 4 H),
3.65 (s, 2 H), 2.17 – 1.95 (m, 4 H), 1.86 – 1.38 (m, 12 H) ppm. 13C-NMR (50 MHz, CDCl3): δ = 165.2 (s,
4 C), 129.4 (d, 2 C), 59.6 (d, 2 C), 43.4 (s, 1 C), 42.0 (t, 2 C), 35.0 (t, 2 C), 29.6 (t, 2 C), 24.6 (t, 2 C),
24.4 (t, 2 C) ppm. Anal. Calcd for C19H24N2O4 (344.41): C 66.26 H 7.02 N 8.13. Found: C 66.21 H 7.30
N 8.09.
Z-Spiro[cyclohexane-1,15’-[3,12]-diazatricyclo[10.3.1.13,14]-7-heptadecene]-2’,13’,16’,17’-tetraone
(14a). Diolefine 8 (500 mg, 1.29 mmol) was converted using Grubbs catalyst 1st generation (110mg, 10
mol%) to give 14a (320 mg, 69%) as colorless crystals. Mp 202-205 °C, TLC: Rf = 0.52 (light
petroleum/EtOAc, 4:1), 1H-NMR (200 MHz, CDCl3): δ = 5.48 – 5.29 (m, 2 H), 3.94 – 3.78 (m, 4 H), 3.90 (s,
2 H), 1.71 – 1.33 (m, 18 H) ppm. 13C-NMR (50 MHz, CDCl3): δ = 165.7 (s, 4 C), 129.1 (d, 2 C), 59.3 (d, 2

HETEROCYCLES, Vol. 71, No. 11, 2007
2341
C), 39.1 (t, 2 C), 36.2 (s, 1 C), 32.7 (t, 2 C), 28.3 (t, 2 C), 25.0 (t, 1 C), 23.3 (t, 2 C), 20.7 (t, 2 C) ppm.
Anal. Calcd for C20H26N2O4 (358.44): C 67.02 H 7.31 N 7.82. Found: C 66.75 H 7.26 N 7.64.
E-Spiro[cyclohexane-1,15’-[3,12]-diazatricyclo[10.3.1.13,14]-7-heptadecene]-2’,13’,16’,17’-tetraone
(14b). Diolefine 8 (200 mg, 0.56 mmol) was converted using Grubbs catalyst 2nd generation (50 mg, 10
mol%) to give 14b (117 mg, 59%) as colorless crystals. Mp 213-215 °C, TLC: Rf = 0.52 (light
petroleum/EtOAc, 4:1), 1H-NMR (200 MHz, CDCl3): δ = 5.25 – 5.13 (m, 2 H), 4.00 – 3.86 (m, 4 H), 3.83
13
(s, 2 H), 2.24 – 2.01 (m, 4 H), 1.90 – 1.73 (m, 4 H), 1.61 – 1.34 (m, 10 H) ppm. C-NMR (50 MHz,
CDCl3): δ = 164.9 (s, 4 C), 129.4 (d, 2 C), 58.5 (d, 2 C), 42.0 (t, 2 C), 36.5 (s, 1 C), 32.5 (t, 2 C), 29.8 (t,
2 C), 25.2 (t, 1 C), 24.8 (t, 2 C), 20.8 (t, 2 C) ppm. Anal. Calcd for C20H26N2O4 (358.44): C 67.02 H 7.31
N 7.82. Found: C 66.77 H 7.53 N 7.73.
Spiro[cyclopentane-1,17’-[3,14]-diazatricyclo[12.3.1.13,16]-8-nonadecene]-2’,15’,18’,19’-tetraone
(15). Diolefine 9 (500 mg, 1.25 mmol) was converted using Grubbs catalyst 1st generation (100mg, 10
mol%) to give 15 (240 mg, 51%) as colorless crystals. Mp 207-209 °C, TLC: Rf = 0.33 (light
petroleum/EtOAc, 4:1), 1H-NMR (200 MHz, CDCl3): δ = 5.41 – 5.09 (m, 2 H), 3.87 – 3.59 (m, 6 H), 2.01
– 0.92 (m, 20 H) ppm. 13C-NMR (50 MHz, CDCl3): δ = 165.4 (s, 4 C), 131.2 (d, 2 C), 59.8 (d, 2 C), 43.0
(s, 1 C), 39.9 (t, 2 C), 35.4 (t, 2 C), 28.5 (t, 2 C), 27.0, (t, 2 C), 26.9, (t, 2 C), 24.4 (t, 2 C) ppm (Z-Isomer).
δ = 165.3 (s, 4 C), 129.4 (d, 2 C), 59.7 (d, 2 C), 42.6 (s, 1 C), 35.2 (t, 2 C), 31.5 (t, 2 C), 28.0 (t, 2 C), 26.9
(t, 2 C), 26.8 (t, 2 C), 24.4 (t, 2 C) ppm (E-Isomer). Anal. Calcd for C21H28N2O4 (372.47): C 67.72 H 7.58
N 7.52. Found: C 67.81 H 7.73 N 7.47.
Spiro[cyclohexane-1,17’-[3,14]-diazatricyclo[12.3.1.13,16]-8-nonadecene]-2’,15’,18’,19’-tetraone (16).
Diolefine 10 (200 mg, 0.48 mmol) was converted using Grubbs catalyst 2nd generation (50 mg, 10 mol%)
to give 16 (142 mg, 66%) as colorless crystals. Mp 176-177 °C, TLC: Rf = 0.53 (light petroleum/EtOAc,
4:1), 1H-NMR (200 MHz, CDCl3): δ = 5.41 – 5.08 (m, 2 H), 3.90 – 3.64 (m, 6 H), 1.98 – 1.72 (m, 4 H),
1.57 – 0.94 (m, 18 H) ppm. 13C-NMR (50 MHz, CDCl3): δ = 165.1 (s, 4 C), 129.4 (d, 2 C), 58.9 (d, 2 C),
39.8 (t, 2 C), 36.1 (s, 1 C), 32.6 (t, 2 C), 28.3 (t, 2 C), 27.0 (t, 2 C), 26.8 (t, 2 C), 25.1 (t, 1 C), 20.7 (t, 2 C)
ppm (Z-Isomer). δ = 165.0 (s, 4 C), 131.2 (d, 2 C), 59.1 (d, 2 C), 39.7 (t, 2 C), 35.7 (s, 1 C), 32.7 (t, 2 C),
28.8 (t, 2 C), 27.0 (t, 2 C), 26.6 (t, 2 C), 25.1 (t, 1 C), 20.7 (t, 2 C) ppm (E-Isomer). Anal. Calcd for
C22H30N2O4 (386.50): C 68.37 H 7.82 N 7.25. Found: C 68.21 H 7.91 N 7.06.
General Procedure for Ring Closing Metathesis Reactions under Microwave Irradiation: 0.3 mmol
of diolefins 5-10 and Grubbs catalyst 2nd generation (25 mg, 10 mol%) were dissolved in dry CH2Cl2 (5

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HETEROCYCLES, Vol. 71, No. 11, 2007
mL) and added to the reaction vessel under dry conditions. The reaction mixture was heated under
microwave irradiation for 7 min at 125 °C. The solvent was evaporated and products 11-16 were purified
by chromatography.
The results of these reactions are summarized in Table 3.
General Procedure for Hydrogenated Tricyclic Compounds 17-20. Metathesis products 13-16 (1.0
equiv.) were hydrogenated with Pd/C (10%) in dry ethanol/dioxane (10 mL) at 60 psi in a Parr apparatus
for 5 h. The reaction mixture was filtered over hyflo, and the solvent was distilled off. The crude product
was purified by chromatography (light petroleum/EtOAc, 3:1).
Spiro[cyclopentane-1,15’-[3,12]-diazatricyclo[10.3.1.13,14]heptadecane]-2’,13’,16’,17’-tetraone (17).
Compound 13b (150 mg, 0.44 mmol) was hydrogenated using Pd/C (15 mg, 10%) to give 17 (150 mg,
98%) as colorless crystals. Mp 202-203 °C, TLC: Rf = 0.50 (light petroleum/EtOAc, 3:1), 1H-NMR (200
MHz, CDCl3): δ = 3.94 – 3.81 (m, 4 H), 3.76 (s, 2 H), 1.80 – 1.36 (m, 12 H), 1.25 – 0.89 (m, 8 H) ppm.
13C-NMR (50 MHz, CDCl3): δ = 165.9 (s, 4 C), 60.2 (d, 2 C), 43.1 (s, 1 C), 39.9 (t, 2 C), 35.3 (t, 2 C),
24.5 (t, 2 C), 24.4 (t, 2 C), 23.6 (t, 2 C), 22.1 (t, 2 C) ppm. Anal. Calcd for C19H26N2O4 (346.43): C 65.88
H 7.56 N 8.09. Found: C 65.81 H 7.38 N 8.06.
Spiro[cyclohexane-1,15’-[3,12]-diazatricyclo[10.3.1.13,14]heptadecane]-2’,13’,16’,17’-tetraone (18).
Compound 14a (500mg, 1.39 mmol) was hydrogenated using Pd/C (50 mg, 10%) to give 18 (463 mg,
93%) as colorless crystals. Mp 217-218 °C, TLC: Rf = 0.53 (light petroleum/EtOAc, 3:1), 1H-NMR (200
MHz, CDCl3): δ = 3.93 – 3.77 (m, 6 H), 1.59 – 1.31 (m, 14 H), 1.26 – 0.87 (m, 8 H) ppm. 13C-NMR (50
MHz, CDCl3): δ = 165.6 (s, 4 C), 59.3 (d, 2 C), 39.7 (t, 2 C), 36.2 (s, 1 C), 32.7 (t, 2 C), 25.1 (t, 1 C), 24.6
(t, 2 C), 23.4 (t, 2 C), 22.1 (t, 2 C), 20.7 (t, 2 C) ppm. Anal. Calcd for C20H28N2O4 (360.46): C 66.64 H
7.83 N 7.77. Found: C 66.36 H 7.71 N 7.68.
Spiro[cyclopentane-1,17’-[3,14]-diazatricyclo[12.3.1.13,16]nonadecane]-2’,15’,18’,19’-tetraone (19).
Compound 15 (150 mg, 0.40 mmol) was hydrogenated using Pd/C (15 mg, 10%) to give 19 (140 mg,
94%) as colorless crystals. Mp 196-198 °C, TLC: Rf = 0.55 (light petroleum/EtOAc, 3:1), 1H-NMR (200
MHz, CDCl3): δ = 3.89 – 3.70 (m, 6 H), 1.80 – 1.27 (m, 12 H), 1.24 – 0.91 (m, 12 H) ppm. 13C-NMR (50
MHz, CDCl3): δ = 165.7 (s, 4 C), 59.7 (d, 2 C), 43.5 (s, 1 C), 40.5 (t, 2 C), 35.1 (t, 2 C), 27.7 (t, 2 C), 26.6
(t, 2 C), 25.5 (t, 2 C), 25.4 (t, 2 C), 24.4 (t, 2 C) ppm. Anal. Calcd for C21H30N2O4 (374.48): C 67.36 H
8.07 N 7.48. Found: C 67.30 H 8.08 N 7.40.

HETEROCYCLES, Vol. 71, No. 11, 2007
2343
Spiro[cyclohexane-1,17’-[3,14]-diazatricyclo[12.3.1.13,16]nonadecane]-2’,15’,18’,19’-tetraone
(20).
Compound 16 (90 mg, 0.23 mmol) was hydrogenated using Pd/C (10 mg, 10%) to give 20 (84 mg, 93%)
as colorless crystals. Mp 181-183 °C, TLC: Rf = 0.79 (light petroleum/EtOAc, 3:2), 1H-NMR (200 MHz,
CDCl3): δ = 3.87 – 3.70 (m, 6 H), 1.58 – 1.29 (m, 14 H), 1.25 – 0.90 (m, 12 H) ppm. 13C-NMR (50 MHz,
CDCl3): δ = 165.0 (s, 4 C), 58.8 (d, 2 C), 40.4 (t, 2 C), 36.6 (s, 1 C), 32.5 (t, 2 C), 28.0 (t, 2 C), 26.7 (t, 2
C), 25.7 (t, 2 C), 25.4 (t, 2 C), 25.1 (t, 1 C), 20.8 (t, 2 C) ppm. Anal. Calcd for C22H32N2O4 (388.51): C
68.01 H 8.30 N 7.21. Found: C 67.74 H 8.36 N 7.09.
General Procedure for Diamines 21-24. To a solution of the appropriate hydrogenated tetraoxo
compound (17-20, 1.0 equiv.) in dry toluene (10% solution) was added sodium
bis(2-methoxyethoxy)aluminium hydride solution (Red-Al®, 65 wt% in toluene, 8.0 equiv.) and the
resulting mixture was refluxed under an argon atmosphere for 15 h. The reaction mixture was hydrolyzed
with NaOH (10% solution) and extracted with toluene for three times. The combined organic layers were
dried over Na2SO4 and the solvent was distilled off. Products were purified by flash column
chromatography (MeOH/NEt3, 3:2).
Spiro[cyclopentane-1,15’-[3,12]-diazatricyclo[10.3.1.13,14]heptadecane] (21). Compound 17 (40 mg,
0.12 mmol) was reduced using Red-Al® solution (0.28 mL, 0.92 mmol) to give 21 (27 mg, 81%) as a
yellow oil. TLC: Rf = 0.68 (MeOH/NEt3, 3:2), 1H-NMR (200 MHz, CDCl3): δ = 2.83 – 2.34 (m, 8 H),
2.25 – 2.04 (m, 4 H), 1.75 – 0.90 (m, 22 H) ppm. 13C-NMR (50 MHz, CDCl3): δ = 60.0 (t, 2 C), 55.7 (t, 4
C), 39.4 (d, 2 C), 37.9 (s, 1 C), 35.1 (t, 2 C), 28.9 (t, 2 C), 27.5 (t, 2 C), 24.6 (t, 2 C), 23.9 (t, 2 C) ppm.
MALDI-MS: m/z= 291.28 [M + H]+ (calcd. for C19H35N2: 291.28).
Spiro[cyclohexane-1,15’-[3,12]-diazatricyclo[10.3.1.13,14]heptadecane] (22). Compound 18 (67 mg,
0.19 mmol) was reduced using Red-Al® solution (0.45 mL, 1.45 mmol) to give 22 (41 mg, 72%) as a
yellow oil. TLC: Rf = 0.64 (MeOH/NEt3, 3:2), 1H-NMR (200 MHz, CDCl3): δ = 2.80 – 2.66 (m, 8 H),
2.34 – 2.21 (m, 4 H), 1.63 – 1.18 (m, 24 H) ppm. 13C-NMR (50 MHz, CDCl3): δ = 58.8 (t, 2 C), 53.8 (t, 4
C), 37.4 (d, 2 C), 33.1 (t, 2 C), 32.7 (s, 1 C), 28.9 (t, 2 C), 27.5 (t, 2 C), 26.6 (t, 1 C), 24.6 (t, 2 C), 20.6
(t, 2 C) ppm. MALDI-MS: m/z= 305.25 [M + H]+ (calcd. for C20H37N2: 305.29).
Spiro[cyclopentane-1,17’-[3,14]-diazatricyclo[12.3.1.13,16]nonadecane] (23). Compound 19 (30 mg,
0.08 mmol) was reduced using Red-Al® solution (0.19 mL, 0.64 mmol) to give 23 (19 mg, 74%) as a yellow
oil. TLC: Rf = 0.70 (MeOH/NEt3, 3:2), 1H-NMR (200 MHz, CDCl3): δ = 2.88 – 2.62 (m, 8 H), 2.30 – 2.07
(m, 4 H), 1.65 – 1.04 (m, 26 H) ppm. 13C-NMR (50 MHz, CDCl3): δ = 59.0 (t, 2 C), 56.1 (t, 4 C), 39.2 (d, 2

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HETEROCYCLES, Vol. 71, No. 11, 2007
C), 38.5 (s, 1 C), 37.9 (t, 2 C), 35.2 (t, 2 C), 27.3 (t, 2 C), 27.2 (t, 2 C), 25. 9 (t, 2 C), 23.7 (t, 2 C) ppm.
MALDI-MS: m/z= 319.32 [M + H]+ (calcd. for C21H39N2: 319.31).
Spiro[cyclohexane-1,17’-[3,14]-diazatricyclo[12.3.1.13,16]nonadecane] (24). Compound 20 (16 mg,
0.04 mmol) was reduced using Red-Al® solution (0.06 mL, 0.33 mmol) to give 24 (9 mg, 68%) as a
yellow oil. TLC: Rf = 0.63 (MeOH/NEt3, 3:2), 1H-NMR (200 MHz, CDCl3): δ = 2.91 – 2.58 (m, 8 H),
2.32 – 2.08 (m, 4 H), 1.78 – 1.18 (m, 28 H) ppm. 13C-NMR (50 MHz, CDCl3): δ = 58.7 (t, 2 C), 54.2 (t, 4
C), 37.3 (d, 2 C), 33.0 (t, 2 C), 32.8 (s, 1 C), 29.7 (t, 2 C), 26.3 (t, 1 C), 25.8 (t, 2 C), 25.5 (t, 2 C), 22.7 (t,
2 C), 20.6 (t, 2 C) ppm. MALDI-MS: m/z= 333.33 [M + H]+ (calcd. for C22H41N2 : 333.33).
X-Ray Crystallographic Study:
General. X-ray data collection was carried out with a Bruker AXS Smart APEX CCD diffractometer and
graphite monochromatized Mo Kα radiation, λ(Mo-Kα) = 0.71073 Å. For each crystal 3-4 sets of frames
were measured to cover at least a hemisphere of the reciprocal space (ω-scans, ∆ω = 0.3°, 20-30 sec per
frame). Corrections for absorption with program SADABS,14 structure solution with direct methods and
program SHELXS97, structure refinement on F2 using the program SHELXL97.15 All non-hydrogen
atoms were refined anisotropically. Hydrogen atoms had isotropic temperature factors and rided on the
C-atoms to which they were bonded. Where necessary, disorder was taken into account by split atom
models. Views of the molecular structures are shown in figs. 1 and 2. Bond lengths and angles show no
unusual features.
Crystal data. 12: C18H24N2O4, Mr = 332.39; orthorhombic, space group Pnma (no. 62), a = 6.829(1) Å, b
= 12.369(2) Å, c = 18.996(2) Å, V = 1604.5(3) Å3, Z = 4, Dc = 1.376 g cm-3, µMo = 0.098 mm-1, T =
297(2) K; Specimen: 0.80 × 0.10 × 0.04 mm; Tmin/max (multiscan absorption correction) = 0.92. θmax
=
25°; Ntotal = 15607, Nunique = 1479 (Rint = 0.044), Nobs (F > 4σ(F)) = 1192; R = 0.065, Rw = 0.178 (all data);
(∆ρF)max = 0.48 e Å-3. The structure shows conformation disorder in the olefin part of the macrocycle.
13a: C19H24N2O4, Mr = 344.40; triclinic, space group P-1 (no. 2), a = 8.371(3) Å, b = 15.251(5) Å, c =
15.514(5) Å, α = 116.335(7)°, β = 94.816(7)°, γ = 90.124(7)°, V = 1767.0(10) Å3, Z = 4, Dc = 1.295 g
cm-3, µMo = 0.091 mm-1, T = 303(2) K; Specimen: 0.61 × 0.28 × 0.06 mm; Tmin/max (multiscan absorption
correction) = 0.92. θmax = 23°; Ntotal = 8152, Nunique = 4897 (Rint = 0.044), Nobs (F > 4σ(F)) = 4897; R =
0.092, Rw = 0.128 (all data); (∆ρF)max = 0.21 e Å-3. There are two independent molecules present in the
structure, both being conformation disordered in the olefin part of the macrocycle.
13b: C19H24N2O4, Mr = 344.40; monoclinic, space group P21 (no. 4), a = 7.234(3) Å, b = 8.898(3) Å, c =
13.891(5) Å, β = 104.48(1)°, V = 865.7(5) Å3, Z = 2, Dc = 1.321 g cm-3, µMo = 0.093 mm-1, T = 303(2) K;
Specimen: 0.60 × 0.35 × 0.20 mm; Tmin/max (multiscan absorption correction) = 0.85. θmax = 25°; Ntotal
=

HETEROCYCLES, Vol. 71, No. 11, 2007
2345
4742, Nunique = 2760 (Rint = 0.025), Nobs (F > 4σ(F)) = 2294; R = 0.078, Rw = 0.189 (all data); (∆ρF)max
=
0.30 e Å-3. Structure ordered. Racemic substance forming a conglomerate, chirality indeterminate in the
present experiment.
CCDC-240073 - 240075 contain the supplementary crystallographic data for this paper. These data can be
obtained free of charge at www.ccdc.cam.ac.uk/conts/retrieving.html [or from the Cambridge Crystallo-
graphic Data Centre, 12, Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336 033; E-mail:
deposit@ccdc.cam.ac.uk].
REFERENCES AND NOTES
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14. Bruker programs: SMART, version 5.630; SAINT, version 7.0; SADABS, version 2.10; XPREP,
version 6.14 (Bruker AXS Inc., Madison, WI, 2001).
15. G. M. Sheldrick (1997). SHELX97. Program system for crystal structure determination. University
of Göttingen.