Convenient synthesis of chiral cyclophanes that can coordinate to metals

Article abstract of DOI:10.1021/ja983907u

Optically pure cyclophanes possessing a 1,3-dicarbonyl moiety were conveniently synthesized from alkanedioyl dichloride in four steps. The intramolecular [4+2]cycloaddition of bis(acylketene)s generated by thermal decomposition of bis(4,6-dioxo-1,3-dioxane) proceeded smoothly, giving cyclophane pyranones in high yields. The compounds possessing 7-10 bridging methylenes were resolved by imine formation with (R)-1-phenylethylamine, followed by basic hydrolysis. These cyclophanes are optically active versions of acetylacetone or salicylaldehyde and formed complexes with metals such as copper and europium. X-ray analysis of the chiral copper complex indicated the pentacoordinated structure of the copper metal with syn configuration of the two bridging chains.

Full text of DOI:10.1021/ja983907u

8270
J. Am. Chem. Soc. 1999, 121, 8270-8276
Convenient Synthesis of Chiral Cyclophanes that Can Coordinate to
Metals
Masayuki Sato,*,† Fumiaki Uehara, Kayo Sato, Masahiko Yamaguchi,* and
Chizuko Kabuto‡
Contribution from the Department of Organic Chemistry, Graduate School of Pharmaceutical Sciences,
Tohoku UniVersity, Aoba, Sendai 980-8578, Japan
ReceiVed NoVember 12, 1998
Abstract: Optically pure cyclophanes possessing a 1,3-dicarbonyl moiety were conveniently synthesized from
alkanedioyl dichloride in four steps. The intramolecular [4+2]cycloaddition of bis(acylketene)s generated by
thermal decomposition of bis(4,6-dioxo-1,3-dioxane) proceeded smoothly, giving cyclophane pyranones in
high yields. The compounds possessing 7-10 bridging methylenes were resolved by imine formation with
(R)-1-phenylethylamine, followed by basic hydrolysis. These cyclophanes are optically active versions of
acetylacetone or salicylaldehyde and formed complexes with metals such as copper and europium. X-ray analysis
of the chiral copper complex indicated the pentacoordinated structure of the copper metal with syn configuration
of the two bridging chains.
Cyclophanes, some of which can be chiral, are an interesting
group of compounds.1 When the ansa chain is sufficiently short,
cyclophanes exhibit planar chirality due to the restricted rotation
of the aromatic ring. The chirality might show chemical and
physical properties different from those of the tetrahedral or
the axial chirality. For example, since an enantioface of the
aromatic ring in the cyclophane is shielded by the ansa chain,
it can provide an effective chiral environment for asymmetric
catalysis. It should also be noted that cyclophanes are a chiral
equivalent of aromatic compounds. Since materials very often
possess aromatic rings in their structure, substitution of such
group with cyclophane converts achiral compounds to chiral,
which can be an interesting approach for chiral materials. Quite
a limited number of reports, however, appeared on the studies
of chiral cyclophanes.2,3 It may be due to the lack of an efficient
synthetic method for optically pure cyclophanes with suitable
functionalities. The syntheses have been rather lengthy, and
therefore, introduction of functionalized groups was not facile.
Described here is a convenient method for synthesizing cyclo-
phanes 1, which have a pyranone ring as the aromatic moiety
(Figure 1). Optically pure 1 can be prepared from commercially
available diacid dichlorides in a few steps using the intramo-
lecular [4+2]cycloaddition of bis(acylketene)s4-6 as the key
step. These cyclophanes possessing a 1,3-dicarbonyl moiety are
a chiral equivalent of acetylacetone or salicylaldehyde and are
capable of coordinating to metals.
Figure 1. Chiral cyclophanes.
Bis(4,6-dioxo-1,3-dioxane)s 4 (n ) 6-12, 16) were synthe-
sized from the corresponding diacid dichlorides 2 (n ) 6-12,
16) and Meldrum’s acid 3 (Scheme 1 and Table 1) in the
presence of pyridine at 0 °C to room temperature.7 Then slow
addition of 4 (n ) 7-12, 16) to refluxing chlorobenzene under
highly diluted conditions (1 × 10-4 M) gave (()-1 (n ) 7-12,
16) generally in high yields. At temperatures higher than 130
°C, 4 (n ) 7-12, 16) lost acetone and carbon dioxide generating
bis(acylketene)s 5 (n ) 7-12, 16),6 which cyclized via [4+2]-
cycloaddition. The high efficiency of the cyclophane formation
may be ascribed to the very rapid reaction rate of the cycload-
dition. The synthesis could be carried out on a 10 mmol scale,
and the cyclophanes (()-1 (n ) 7-11) were readily separated
from oligomeric compounds by distillation. Higher homologues
(()-1 (n ) 12, 16) were isolated by chromatography on neutral
silica gel, which contains a lower quantity of metal cations
compared to the usual silica gel. Chromatography of 1 on the
latter resulted in strong adsorption, and 1 was obtained as an
orange material, probably due to chelation with metal cations
† School of Pharmaceutical Sciences, University of Shizuoka, Yada,
Shizuoka 422-8526, Japan.
‡ Instrumental Analysis Center for Chemistry, Graduate School of
Science, Tohoku University, Aoba, Sendai 980-8578, Japan.
(1) Review. Cram, D. J.; Cram, J. M. Acc. Chem. Res. 1971, 4, 204.
Bodwell, G. J. Angew. Chem., Int. Ed. Engl. 1996, 35, 2085.
(2) Asymmetric synthesis. Tachibana, Y.; Ando, M.; Kuzuhara, H. Chem.
Lett. 1982, 1765. Reich, H. J.; Yelm, K. E. J. Org. Chem. 1991, 56, 5672.
Antonov, D. Y.; Belokon, Y. N.; Ikonnikov, N. S.; Oelova, S. A.; Pisarevsky,
A. P.; Raevski, N. I.; Rozenberg, V. I.; Sergeeva, E. V.; Stuchkov, Y. T.;
Tararov, V. I.; Vorontsov, E. V. J. Chem. Soc., Perkin Trans I 1995, 1873.
Kanomata, N.; Nakata, T. Angew. Chem., Int. Ed. Engl. 1997, 36, 1207.
Pye, P. J.; Rossen, K.; Reamer, R. A.; Tsou, N. N.; Volante, R. P.; Reider,
P. J. J. Am. Chem. Soc. 1997, 119, 6207.
(4) Reviews for acylketene: Tidwell, T. T. Ketenes; John Wiley &
Sons: New York, 1995. Wentrup, C.; Heilmayer, W.; Kollenz, G. Synthesis
1994, 1219. Kaneko, C.; Sato, M.; Sakaki, J.; Abe, Y. J. Heterocycl. Chem.
1990, 27, 25.
(5) Carrol, M. F.; Bader, A. R. J. Am. Chem. Soc. 1952, 74, 6305. Carrol,
M. F.; Bader, A. R. J. Am. Chem. Soc. 1953, 75, 5400. Ja¨ger, G.;
Wenzelbuger, J. Liebigs Ann. Chem. 1976, 1689.
(6) Sato. M.; Ogasawara, H.; Kato, T. Chem. Pharm. Bull. 1984, 32,
2602. Sato. M.; Sekiguchi, K.; Ogasawara, H.; Kaneko, C. Synthesis 1985,
224. Sato. M.; Yoneda, N.; Katagiri, N.; Watanabe, N.; Kaneko, C. Synthesis
1986, 672. Sato, M.; Ban, H.; Kaneko, C. Tetrahedron Lett. 1997, 38, 6689.
(7) Oikawa, Y.; Sugano, K.; Yonemitsu, O. J. Org. Chem. 1978, 43,
2087.
(3) Chiral polymer. Fiesel, R.; Huber, J.; Scherf, U. Angew. Chem., Int.
Ed. Engl. 1996, 35, 2111.
10.1021/ja983907u CCC: $18.00 © 1999 American Chemical Society
Published on Web 08/31/1999

Chiral Cyclophanes that Can Coordinate to Metals
J. Am. Chem. Soc., Vol. 121, No. 36, 1999 8271
Scheme 1
Figure 2. ORTEP drawing of (R,R)-6 (n ) 10) along with the atomic
numbering scheme. Thermal ellipsoids are drawn at the 30% probability
level.
Scheme 2
(n ) 6, 7, 8) and 7b (n ) 6, 7, 8), while such dimers were not
detected in the higher homologues (Table 1, Scheme 2). The
structures of 7a (n ) 8) and 7b (n ) 8) were determined by
chemical transformations: The treatment of 7a (n ) 8) with
90% sulfuric acid at 130 °C gave pyranonenonanoic acid 8.
Bis(pyranone) 9 and decanedioic acid 10 were obtained from
7b (n ) 8).
The cyclophanes (()-1 (n ) 7-10) were resolved by
treatment with (R)-1-phenylethylamine, followed by chromato-
graphic separation to give diastereomeric imines (S,R)-6 (n )
7-10) and (R,R)-6 (n ) 7-10) (Scheme 1 and Table 1).
Although diastereomeric imines (S,R)-6 (n ) 11) and (R,R)-6
(n ) 11), which possessed a longer ansa chain, could be
observed by 1H NMR, they were not stable enough to be
separated at room temperature. TLC of this mixture showed
two spots only when the chromatography was conducted at -15
°C. A single imine compound was obtained from 6 (n ) 12,
16). The relationship between the bridging chain length and the
stability of the planar chirality is similar to that of known
benzene and pyridine cyclophanes.8 The configuration of (R,R)-6
(n ) 10) was determined by X-ray crystallographic analysis
based on the (R)-configuration of the amine moiety (Figure 2
and Table 2).
Table 1. Synthesis of Chiral Cyclophanes
yield (%)
n
4
(()-1
7a/7b
(R,R)-6/(S,R)-6
(R)-1
(S)-1
6
76
88
74
74
75
71
70
87
18 (1:1)a
28 (1:1)a
6 (1:1)a
7
8
27
68
88
90
87
82
83
41:43
41:36
41:40
50:48
57:43b
99
100
85
92
100
97
9
10
11
12
16
87
99
a Isomer ratio is shown in parentheses. b The diastereomers were
1
detected by H NMR, although not isolable.
such as Fe3+. The observations indicated the high affinity of 1
toward metals.
The yield of (()-1 (n ) 7) decreased, and (()-1 (n ) 6)
could not be obtained under the present reaction conditions,
which presumably was due to their strained nature. One of the
bridging methylene protons of (()-1 (n ) 7) appeared at δ 0.18
in 1H NMR spectra, reflecting the close proximity of the proton
to the pyranone ring. Dimeric products were obtained in the
reactions of (()-4 (n ) 6, 7, 8) as mixtures of two isomers 7a
(8) For example, see, Lu¨ttringhaus, A.; Eyring, G. Liebigs Ann. Chem.
1957, 604, 111. Blomquist, A. T.; Roland, E. S.; Meinwald, Y. C.; Smith,
B. H. J. Org. Chem. 1961, 26, 1687. Nakazaki, M.; Yamamoto, K.;
Okamoto, S. Tetrahedron Lett. 1969, 4597.

8272 J. Am. Chem. Soc., Vol. 121, No. 36, 1999
Sato et al.
Table 2. Summary of Crystal Data, Data Collection, and Refinement Details
compound
formula
formula weight
(R,R)-6 (n ) 10)
(R,R)-16 (n ) 8)‚acetone
(R,R)-16 (n ) 9)
CuC30H40O9
608.19
C24H31O3N
CuC31H42O10
381.51
628.21
crystal size; mm
crystal system; space group
0.4 × 0.5 × 0.5
0.2 × 0.3 × 0.7
0.3 × 0.3 × 0.5
orthorhombic; P212121
orthorhombic; P212121
orthorhombic; P212121
temp, K
a, Å
b, Å
c, Å
293
13.469 (3)
14.966 (3)
10.73 (1)
2163 (2)
4
1.171
0.76
150
11.498 (1)
28.745 (5)
9.346 (1)
3088.8 (7)
4
1.372
7.62
150
13.979 (2)
15.684 (1)
13.385 (1)
2934.6 (5)
4
1.376
7.96
V, Å3
Z
D
calcd, g/cm3
µ (MoKR), cm-1
scan mode
2θ-ω
ω
2θ-ω
absorption correction
independent reflections
no. of obsd data [critical]
no. of variables
Ψ scans (0.951 < T < 1.000)
Ψ scans (0.858 < T < 1.000)
Ψ scans (0.815 < T < 1.000)
2438 (2θ max ) 52°)
4288 (2θ max ) 58°)
4735 (2θ max ) 60°)
1252 [Io > 2σ(Io)]
3451 [Io > 3σ(Io)]
3897 [Io > 3σ(Io)]
253
380
522
R ) Σ||Fo| - |Fc||/Σ|Fo|
(∆F max), eÅ3
goodess of fit
0.069
0.059
0.19
2.03
0.051
0.053
0.42
2.49
0.034
0.034
0.30
1.89
Rw ) [Σw(|Fo| - |Fc|)2/ΣwFo ]1/2
2
(()-o-15 in a high yield. Resolution was conducted as in the
case of 1 to give (R)-o-15 and (S)-o-15 as configurationally
stable compounds. The absolute configuration was determined
by the similarity of the CD spectra to 1 (Figure 3). The
corresponding meta and para derivatives, (()-m-15 and (()-
p-15, were also prepared from 1,3- and 1,4-benzenedialdehyde,
m-11 and p-11, respectively. However, the diastereomeric imines
of m-11 and p-11 with (R)-1-phenylethylamine epimerized at
room temperature.
The optically active cyclophanes 1 formed complexes with
metals.10 When (R)-1 (n ) 8-10) were treated with Cu(OAc)2
in aqueous ethanol at room temperature, blue copper complexes
Cu[(R)-1]2, (R,R)-16 (n ) 8-10) were obtained in quantitative
yields. X-ray analyses of the (R,R)-16 (n ) 8,9) showed that
the two carbonyl oxygens occupied the trans position, and
consequently, the bridging methylenes of the two ligands were
in syn relationship (Figure 4). A water molecule occupied the
apical position of (R,R)-16 (n ) 8, 9) anti to the bridging
methylene, suggesting the Lewis acid character of the copper
complexes. The molecules had roughly 2-fold axis symmetry
through the apical Cu-O9(water) bond. While bis(acetylaceto-
nato)- and bis(salicylaldehydato)copper complexes were reported
to exhibit the ideal square planar coordination,11,12 (R,R)-16 (n
) 8,9) possessed a five-coordinate Cu atom including coordina-
tion of a water molecule. The four oxygen atoms, O1, O2, O3,
and O4, were not planar and deviated in the range of -0.280
to +0.285 Å for (R,R)-16 (n ) 8) and -0.341 to +0.02 Å for
(R,R)-16 (n ) 9). The geometry was not the ideal trigonal-
bipyramidal either. While the axial O1-Cu-O4 angles were
close to 180° (178.3° in (R,R)-16 (n ) 8) and 174.9° in (R,R)-
16 (n ) 9)), the equatorial O2-Cu-O3 angles were not 120°
(147.3° in (R,R)-16 (n ) 8) and 152.5° in (R,R)-16 (n ) 9)).
Thus (R,R)-16 (n ) 8, 9) had an intermediate geometry between
square-pyramidal and trigonal-bipyramidal. Such distortion may
be conveniently described by the geometrical parameter τ
defined as [(O1-Cu-O4) - (O2-Cu-O3)]/60, being τ ) 0
Figure 3. CD spectra of (R)-1 (n ) 7, 8, 9, 10) and (R)-o-15 at the
concentration of 0.082, 0.072, 0.076, 0.061, and 0.050 mM, respectively.
The spectra of (R)-1 (n ) 7, 8, 9, 10) were obtained in hexane and
(R)-o-15 in actonitrile.
The amine moiety of (S,R)-6 (n ) 8-10) and (R,R)-6 (n )
8-10) was removed by alkali treatment at room temperature
for 20 h to give (S)-1 (n ) 8-10) and (R)-1 (n ) 8-10),
respectively, without racemization (Scheme 1 and Table 1). In
the cases of (S,R)-6 (n ) 7) and (R,R)-6 (n ) 7), however,
partial racemization took place under these conditions, which
may be caused by the hydrolysis of the lactone moiety. The
racemization could be suppressed when the reaction was stopped
after 2 h. The absolute configurations of (R)-1 (n ) 7-9) were
determined by comparing their CD spectra with that of (R)-1
(n ) 10), which was derived from (R,R)-6 (n ) 10) (Figure 3).
The CD spectra were very similar independent of the ansa chain
length. The chirality of these cyclophanes was thermally stable,
and no racemization took place in (R)-1 (n ) 10) even in
refluxing methylcyclohexane for 1 h.
Another optically active cyclophane o-15, which possessed
an ortho-phenylene ansa chain, was synthesized from 1,2-
benzenedialdehyde o-11 (Scheme 3). The aldehyde o-11 was
converted to 1,2-benzenedipentanoic acid o-12 by a synthetic
process involving the Wittig-Horner reaction. Then, condensa-
tion with the Meldrum’s acid 3 gave bis(dioxanedione) o-13 in
82% yield, which was transformed into bis(dioxinone) o-14 by
heating in the presence of acetone. It turned out that crystalline
o-14 was easier to purify than o-13. The dioxinone o-14 also
decomposed to acylketene in refluxing chlorobenzene9 and gave
(9) Sato, M.; Ogasawara, H.; Oi, K.; Kato, T. Chem. Pharm. Bull. 1983,
31, 1896.
(10) For example, see Collie, J. N. J. Chem. Soc. 1891, 59, 617. Sitran,
S.; Fregona, D.; Faraglia, G. J. Coord. Chem. 1990, 22, 229.
(11) Lebrun, P. C.; Lyon, W. D.; Kuska, H. A. J. Crystallogr. Spectrosc.
Res. 1986, 6, 889.
(12) Elmali, A.; Elerman, Y.; Svoboda, I.; Fuess, H. Z. Kristallogr. 1995,
210, 612.

Chiral Cyclophanes that Can Coordinate to Metals
J. Am. Chem. Soc., Vol. 121, No. 36, 1999 8273
Scheme 3
Figure 4. ORTEP drawing of (R,R)-16 (n ) 8)‚acetone and (R,R)-16
(n ) 9) along with the atomic numbering scheme. Atoms of solvent
are drawn at the ideal sphere for clarity. Thermal ellipsoids are drawn
at the 30% probability level. Selected bond lengths (Å) and bond angles
(deg) at metal atom: for (R,R)-16 (n ) 8), Cu-O1 ) 1.912(4), Cu-
O2 ) 1.958(4), Cu-O3 ) 1.957(4), Cu-O4 ) 1.915(4), Cu-O9 )
2.213(4), O1-Cu-O4 ) 178.3(2), O2-Cu-O3 ) 147.3(2), O2-Cu-
O9 ) 104.0(2), O3-Cu-O9 ) 108.7(2); for (R,R)-16 (n ) 9), Cu-
O1 ) 1.914(2), Cu-O2 ) 1.948(2), Cu-O1 ) 1.943(3), Cu-O1 )
1.910(2), Cu-O9 ) 2.207(3), O1-Cu-O4 ) 174.9(1), O2-Cu-O3
) 152.5(1), O2-Cu-O9 ) 103.6(1), O3-Cu-O9 ) 103.9(1).
In summary, a series of optically pure cyclophanes that can
chelate metals were prepared in a few steps using convenient
starting materials and reagents. The [4 + 2]cycloaddition of
acylketene turned out to be a powerful method for the synthesis
of cyclophanes. Various applications of chiral metal complexes
derived from the cyclophanes are conceivable, which includes
asymmetric catalysts, chiral stationary phases, optical, electronic,
or magnetic materials.
for the ideal square-pyramidal and τ ) 1 for the trigonal-
bipyramidal.13 The calculated τ values were 0.42 for (R,R)-16
(n ) 8) and 0.37 for (R,R)-16 (n ) 9), implying that the
geometry was distorted from the square-pyramidal toward the
trigonal-bipyramidal by 42% and 37%, respectively. We con-
sider that the distorted five-coordination reflects constraint at
the Cu atom caused by the ansa chain. Imines (R,R)-6 (n ) 9)
and (S,R)-6 (n ) 9) also formed copper complexes Cu[(R,R)-6
(n ) 9)]2, (R,R,R,R)-17 (n ) 9), and Cu[(S,R)-6 (n ) 9)]2,
(S,R,S,R)-17 (n ) 9), respectively, by the treatment with Cu-
(OTf)2 and triethylamine in THF. Notably, the physical proper-
ties of the diastereomers differed considerably. While the
solution of the former complex in CH2Cl2 was blue (λmax at
558 nm), the latter solution exhibited green color (λmax at 642
nm). Europium complexes Eu[(R)-1 (n ) 8-10)]3, (R,R,R)-18
(n ) 8-10) were obtained from (R)-1 (n ) 8-10) and EuCl3
in the presence of 2 M KOH. The optically active europium
complexes exhibited strong red fluorescence.
Experimental Section
1,8-Bis(2,2-dimethyl-4,6-dioxo-1,3-dioxane-5-yl)octane-1,8-di-
one, 4 (n ) 6). Under an argon atmosphere, a solution of hexanedi-
carboxyl dichloride 2 (n ) 6) (11.95 g, 0.05 mol) in dichloromethane
(50 mL) was added dropwise to a stirred solution of Meldrum’s acid
3 (14.4 g, 0.10 mol) and pyridine (19.75 g, 0.25 mol) in dichloromethane
(200 mL) under ice-cooling over 15 min. The mixture was stirred for
30 min at the temperature and then for 2 h at room temperature. The
mixture was acidified with 10% hydrochloric acid, and dichloromethane
was removed in vacuo. Separated crystals were filtered, washed with
water, and dried. Recrystallization from a mixture of dichloromethane
and ether gave yellowish needles of 4 (n ) 6) (16.2 g, 76%). Mp 94-
(13) Addison, A. W.; Rao, T. N.; Reedijk, J.; van Rijn, J.; Verschoor,
G. C. J. Chem. Soc., Dalton Trans. 1984, 1349.

8274 J. Am. Chem. Soc., Vol. 121, No. 36, 1999
Sato et al.
98 °C. Anal. calcd for C20H26O10: C, 56.32%; H, 6.15%. Found: C,
prisms of mp 62-65 °C (pentane). Anal. calcd for C18H26O4: C,
70.54%; H, 8.56%. Found: C, 70.15%; H, 8.52%. MS (EI) m/z 306
(M+, 100%), 288 (33%), 181 (48%), 69 (45%). IR (CHCl3) 1731, 1637,
1557 cm-1. 1H NMR (400 MHz, CDCl3) δ 1.00-1.40 (18H, m), 1.76
(4H, m), 2.50 (2H, m), 5.97 (1H, s), 16.84 (1H, s). 13C NMR (100
MHz, CDCl3) δ 25.5, 26.0, 26.9, 27.5, 27.6, 27.7, 28.3, 28.6, 28.7,
29.2, 34.7, 39.5, 100.2, 102.0, 160.9, 172.3, 180.7, 209.4.
56.33%; H, 6.37%. IR (CHCl3) 2941, 2861, 1735, 1662, 1570 cm-1
.
1H NMR (400 MHz, CDCl3) δ 1.47 (4H, m), 1.67 (4H, m), 1.74 (12H,
s), 3.07 (4H, t, J ) 7.6 Hz), 15.30 (2H, s). 13C NMR (100 MHz, CDCl3)
δ 25.9, 26.9, 29.0, 35.7, 91.3, 104.7, 159.9, 170.3, 197.6.
(()-15-Hydroxy-13-oxabicyclo[10.2.2]tetradecane-1(15),12(16)-
diene-2,14-dione, (()-1 (n ) 9). Under an argon atmosphere, chlo-
robenzene (1 L) was boiled on an oil bath until about 50 mL of
chlorobenzene was distilled off. Then, a solution of 4 (n ) 9) (4.68 g,
10 mmol) in chlorobenzene (50 mL) was added dropwise under reflux
by a syringe pump for over 20 h. The solution was heated at reflux for
an additional 30 min, and then the solvent was evaporated in vacuo.
The residue was distilled by Kugelrohr to give (()-1 (n ) 9) (2.38 g,
90%). Colorless prisms of mp 92-93 °C (hexane). Bp 122 °C/0.23
mm Hg. Anal. calcd for C15H20O4: C, 68.18%; H, 7.58%. Found: C,
68.18%; H, 7.61%. MS (EI) m/z 264 (M+, 100%), 165 (92%), 69 (58%).
(()-22-Hydroxy-20-oxabicyclo[17.2.2]tricosane-1(22),19(23)-di-
ene-2,21-dione, (()-1 (n ) 16). Purified by column chromatography
on neutral silica gel (Silica Gel 60 N, 40-100 µm, Kanto Chemical
CO., INC.) using hexane/ethyl acetate (10:1) as an eluent. Yellowish
oil. MS (EI) m/z 362 (M+, 95%), 181 (56%), 69 (63%). High-resolution
MS m/z (M+) calcd C22H34O4: 362.2455. Found: 362.2439. IR (neat)
1
1742, 1636, 1556 cm-1. H NMR (400 MHz, CDCl3) δ 1.20-1.35
(22H, m), 1.34 (2H, m), 1.69 (4H, m), 2.53 (2H, dd, J ) 6.4, 6.4 Hz),
3.05 (2H, t, J ) 7.2 Hz), 5.93 (1H, s), 16.99 (1H, s). 13C NMR (100
MHz, CDCl3) δ 25.0, 26.1, 27.3, 27.7, 28.0, 28.1, 28.1, 28.2, 28.3,
28.3, 28.5, 29.0, 29.1, 29.2, 34.2, 40.8, 99.4, 101.5, 160.5, 172.5, 181.3,
208.6.
General Procedures for the Preparation of Imine (R,R)-6 and
(S,R)-6. Under an argon atmosphere, a solution of (()-1 (5.0 mmol)
and (R)-1-phenylethylamine (5.0 mmol) in benzene (30 mL) was
refluxed for 1 h. After evaporation of the solvent, the residue was
purified by column chromatography on neutral silica gel using hexane/
ethyl acetate (5:1) as an eluent to give first (R,R)-6 and then (S,R)-6 as
crystals. (R,R)-6 (n ) 7) and (S,R)-6 (n ) 7) were separated by TLC
over silica gel using chloroform as a developing solvent.
1
IR (CHCl3) 1733, 1633, 1557 cm-1. H NMR (400 MHz, CDCl3) δ
0.68 (1H, m), 0.81 (2H, m), 1.13 (1H, m), 1.20-1.60 (8H, m), 2.01
(2H, m), 2.34 (1H, ddd, J ) 13.6, 12.2, 6.6 Hz), 2.53 (2H, t, J ) 6.2
Hz), 3.61 (1H, ddd, J ) 13.6, 4.6, 4.6 Hz), 6.03 (1H, s), 14.89 (1H, s).
13C NMR (100 MHz, CDCl3) δ 23.5, 24.9, 26.6, 27.4, 27.5, 27.8, 28.0,
34.9, 41.2, 100.2, 101.3, 161.1, 173.8, 177.6, 207.6.
(()-13-Hydroxy-11-oxabicyclo[8.2.2]tetradecane-1(13),10(14)-di-
ene-2,12-dione, (()-1 (n ) 7). Colorless prisms of mp 99-100 °C
(hexane). Bp 117 °C/0.27 mm Hg. Anal. calcd for C13H16O4: C,
66.10%; H, 6.78%. Found: C, 66.02%; H, 6.81%. MS (EI) m/z 236
(M+, 62%), 165 (100%), 69 (62%). IR (CHCl3) 1738, 1627, 1549 cm-1
.
1H NMR (400 MHz, CDCl3) δ 0.18 (1H, m), 1.00-1.40 (6H, m), 1.55
(1H, m), 2.01 (2H, m), 2.35 (1H, ddd, J ) 12.4, 6.6, 2.2 Hz), 2.53
(1H, ddd, J ) 12.4, 10.0, 5.6 Hz), 2.62 (1H, ddd, J ) 12.4, 5.6, 3.8
Hz), 3.63 (1H, dt, J ) 12.4, 3.2 Hz), 6.05 (1H, s), 13.60 (1H, br s).
13C NMR (100 MHz, CDCl3) δ 26.4, 27.5, 29.4, 29.6, 29.8, 34.5, 39.5,
102.0, 102.5, 162.1, 175.5, 176.2, 204.2.
(R,R)- and (S,R)-2-[1-(Phenylethyl)amino]-11-oxabicyclo[8.2.2]-
tetradecane-1(2),10(14)-diene-12,13-dione, (R,R)-6 (n ) 7) and
(S,R)-6 (n ) 7). (R,R)-6 (n ) 7): Colorless prisms of mp 161-162
°C (hexane-dichloromethane). Anal. calcd for C21H25NO3: C, 74.30%;
H, 7.43%; N, 4.13%. Found: C, 74.05%; H, 7.14%; N, 4.06%. MS
(EI) m/z 339 (M+, 39%), 234 (8%), 105 (100%). IR (neat) 1708, 1639,
1
1580 cm-1. H NMR (400 MHz, CDCl3) δ 0.90 (1H, m), 1.07 (1H,
(()-14-Hydroxy-12-oxabicyclo[9.2.2]pentadecane-1(14),11(15)-di-
ene-2,13-dione, (()-1 (n ) 8). Colorless prisms of mp 41-42 °C
(pentane). Bp 115 °C/0.35 mm Hg. Anal. calcd for C14H18O4: C,
67.17%; H, 7.25%. Found: C, 66.91%; H, 7.34%. MS (EI) m/z 250
m), 1.21 (1H, m), 1.45 (5H, m), 1.64 (3H, d, J ) 6.8 Hz), 1.92 (2H,
m), 2.44 (3H, m), 3.66 (1H, m), 4.76 (1H, dq, J ) 7.0, 6.8 Hz), 5.79
(1H, s), 7.31 (5H, m), 11.96 (1H, br s). 13C NMR (100 MHz, CDCl3)
δ 24.4, 27.0, 27.3, 27.9, 28.2, 29.5, 29.7, 33.8, 53.8, 99.0, 109.0, 125.4,
(M+, 43%), 165 (100%), 69 (60%). IR (neat) 1738, 1631, 1555 cm-1
.
1H NMR (400 MHz, CDCl3) δ 0.81 (1H, m), 1.02 (2H, m), 1.13 (3H,
m), 1.34 (2H, m), 1.61 (1H, m), 1.70-1.90 (3H, m), 2.34 (1H, ddd, J
) 13.2, 8.0, 5.6 Hz), 2.43 (1H, ddd, J ) 13.2, 6.6, 6.6 Hz), 2.68 (1H,
ddd, J ) 13.2, 5.6, 5.6 Hz), 3.59 (1H, ddd, J ) 13.2, 8.1, 5.1 Hz),
6.03 (1H, s), 14.11 (1H, br s). 13C NMR (100 MHz, CDCl3) δ 23.2,
25.8, 26.1, 26.8, 27.1, 29.6, 34.0, 37.6, 101.8, 103.6, 161.8, 173.8, 175.9,
206.0.
127.8, 129.0, 141.8, 164.7, 169.0, 173.0, 182.5. [R]24 -34.1 (c 1,
D
CHCl3). CD (0.034 mM, CH3CN) 274.4 nm (∆ꢀ ) +28.63), 252.4
(∆ꢀ ) -2.85), 240.6 (∆ꢀ ) +4.95), 219.2 (∆ꢀ ) -9.79). (S,R)-6 (n
) 7). Colorless prisms of mp 144-145 °C (hexane-dichloromethane).
Anal. calcd for C21H25NO3: C, 74.30%; H, 7.43%; N, 4.13%. Found:
C, 74.02%; H, 7.31%; N, 4.11%. MS (EI) m/z 339 (M+, 38%), 234
1
(7%), 105 (100%). IR (neat) 1706, 1639, 1578 cm-1. H NMR (400
(()-16-Hydroxy-14-oxabicyclo[11.2.2]heptadecane-1(16),13(17)-
diene-2,15-dione, (()-1 (n ) 10). Colorless prisms of mp 73-75 °C
(pentane). Bp 130 °C/0.30 mm Hg. Anal. calcd for C16H22O4: C,
69.06%; H, 7.91%. Found: C, 68.81%; H, 7.97%. MS (EI) m/z 278
MHz, CDCl3) δ 0.47 (1H, m), 0.75 (2H, m), 1.20-1.60 (6H, m), 1.67
(3H, d, J ) 6.8 Hz), 1.87 (1H, m), 2.41 (2H, m), 2.58 (1H, m), 3.75
(1H, m), 4.91 (1H, dq, J ) 7.6, 6.8 Hz), 5.79 (1H, s), 7.34 (5H, m),
12.09 (1H, br s). 13C NMR (100 MHz, CDCl3) δ 24.9, 26.4, 27.0, 27.5,
28.0, 29.1, 29.2, 33.8, 54.4, 99.1, 109.0, 125.4, 127.7, 129.0, 141.9,
164.8, 169.0, 172.9, 182.2. [R]22D -80.2 (c 1, CHCl3). CD (0.035 mM,
CH3CN) 276.2 nm (∆ꢀ ) -29.39), 251.0 (∆ꢀ ) +15.75), 231.4 (∆ꢀ
) +12.18), 214.6 (∆ꢀ ) -12.47).
(M+, 80%), 165 (73%), 69 (60%). IR (CHCl3) 1724, 1636, 1555 cm-1
.
1H NMR (400 MHz, CDCl3) δ 0.96-1.21 (10H, m), 1.36 (1H, m),
1.52 (1H, m), 1.76 (4H, m), 2.34 (2H, ddd, J ) 13.6, 11.2, 4.8 Hz),
2.67 (1H, ddd, J ) 13.6, 4.8, 4.8 Hz), 4.00 (1H, ddd, J ) 12.4, 11.2,
4.8 Hz), 5.99 (1H, s), 16.02 (1H, s). 13C NMR (100 MHz, CDCl3) δ
24.9, 25.7, 27.1, 27.2, 27.4, 27.4, 28.8, 29.2, 34.8, 36.7, 101.9, 102.4,
161.4, 172.5, 178.8, 209.0.
General Procedures for the Preparation of (R)- and (S)-1 by
Hydrolysis. A solution of (R,R)-6 or (S,R)-6 (1.0 mmol) and KOH
(225 mg, 4.0 mmol) in THF (5 mL)-H2O (5 mL) was stirred for 20 h
(2 h in case of (R,R)-6 (n ) 7) or (S,R)-6 (n ) 7)) at room temperature.
The mixture was acidified with 10% hydrochloric acid and then
extracted with ether. The organic layer was washed with brine, dried
over MgSO4, and concentrated. The residue was purified by column
chromatography on neutral silica gel using hexane/ethyl acetate (10:1)
as an eluent to give (R)-1 or (S)-1 as crystals. The optical purity was
determined to be >99% by chiral HPLC analysis using Chiralcel OD
(hexane/2-propanol/trifluoroacetic acid ) 99:1:1). (R)-1 (n ) 7):
(()-17-Hydroxy-15-oxabicyclo[12.2.2]octadecane-1(17),14(18)-di-
ene-2,16-dione, (()-1 (n ) 11). Colorless prisms of mp 77-78 °C
(pentane). Bp 126 °C/0.23 mm Hg. Anal. calcd for C17H24O4: C,
69.86%; H, 8.22%. Found: C, 69.85%; H, 8.22%. MS (EI) m/z 292
(M+, 100%), 181 (47%), 165 (60%). IR (CHCl3) 1731, 1636, 1556
1
cm-1. H NMR (400 MHz, CDCl3) δ 1.00 (4H, m), 1.10-1.40 (10H,
m), 1.61 (2H, m), 1.89 (2H, m), 2.31 (2H, m), 2.70 (1H, ddd, J )
13.6, 6.0, 3.6 Hz), 3.87 (1H, ddd, J ) 11.6, 7.6, 4.4 Hz), 5.97 (1H, s),
16.32 (1H, s). 13C NMR (100 MHz, CDCl3) δ 24.4, 24.9, 26.0, 26.2,
27.1, 27.2, 27.4, 27.8, 28.0, 34.7, 40.5, 100.0, 102.1, 160.9, 172.5, 179.7,
208.9.
(()-18-Hydroxy-16-oxabicyclo[13.2.2]nonadecane-1(18),15(19)-
diene-2,17-dione, (()-1 (n ) 12). Purified by column chromatography
on neutral silica gel (Silica Gel 60 N, 40-100 µm, Kanto Chemical
CO., INC.) using hexane/ethyl acetate (10:1) as an eluent. Colorless
colorless needles of mp 89-91 °C (pentane). [R]23 -290.9 (c 1,
D
CHCl3). CD (0.082 mM, hexane) 326.6 nm (∆ꢀ ) -9.46), 260.8 (∆ꢀ
) +16.31), 237.4 (∆ꢀ ) -19.84). (S)-1 (n ) 7): yield, 92%. Colorless
needles of mp 86-88 °C (pentane). [R]24 +281.1 (c 1, CHCl3). CD
D
(0.084 mM, hexane) 327.8 nm (∆ꢀ ) +10.20), 260.4 (∆ꢀ ) -18.44),
237.4 (∆ꢀ ) +21.51). (R)-1 (n ) 8): colorless needles of mp 74-75
°C (pentane). [R]22 -250.6 (c 1, CHCl3). CD (0.072 mM, hexane)
D

Chiral Cyclophanes that Can Coordinate to Metals
J. Am. Chem. Soc., Vol. 121, No. 36, 1999 8275
325.0 nm (∆ꢀ ) -11.31), 256.2 (∆ꢀ ) +20.23), 235.2 (∆ꢀ ) -19.76)
219.0 (∆ꢀ ) +1.45), 213.0 (∆ꢀ ) -0.84). (S)-1 (n ) 8): colorless
°C (hexane-dichloromethane). Anal. calcd for C28H31NO3: C, 78.29%;
H, 7.27%; N, 3.26%. Found: C, 78.18%; H, 7.33%; N, 3.14%. High-
resolution MS m/z calcd for C28H31NO3 (M+): 429.2304. Found:
needles of mp 75-76 °C (pentane). [R]21 +252.2 (c 1, CHCl3). CD
D
1
429.2305. IR (CHCl3) 1696, 1650, 1574 cm-1. H NMR (400 MHz,
(0.077 mM, hexane) 325.0 nm (∆ꢀ ) +12.72), 256.0 (∆ꢀ ) -19.89),
235.8 (∆ꢀ ) +22.36) 219.6 (∆ꢀ ) +0.64), 213.6 (∆ꢀ ) +2.84). (R)-1
CDCl3) δ 0.88 (1H, m), 1.24-1.60 (3H, m), 1.63 (3H, d, J ) 6.8 Hz),
1.65-2.11 (5H, m), 2.27 (1H, m), 2.42-2.58 (4H, m), 2.71 (1H, m),
3.71 (1H, m), 4.90 (1H, dq, J ) 6.8, 6.8 Hz), 5.72 (1H, s), 7.05-7.13
(4H, m), 7.23 (5H, m), 13.77 (1H, brs). 13C NMR (100 MHz, CDCl3)
δ 24.3, 26.0, 27.4, 27.8, 28.6, 29.9, 32.8, 33.8, 33.9, 54.6, 97.5, 108.9,
125.5, 125.9, 126.1, 127.9, 128.0, 129.2. 129.4, 139.6, 140.2, 141.7,
163.9, 165.7, 176.5, 183.1. [R]24D -26.6 (c 1, CHCl3). CD (0.035 mM,
CH3CN) 335.2 nm (∆ꢀ ) -12.61), 269.4 (∆ꢀ ) +14.75), 222.4 (∆ꢀ
) -5.05). (S,R)-Imine: colorless prisms of mp 174-175 °C (hexane-
dichloromethane). Anal. calcd for C28H31NO3: C, 78.29%; H, 7.27%;
N, 3.26%. Found: C, 78.32%; H, 7.30%; N, 3.29%. High-resolution
MS m/z calcd for C28H31NO3 (M+): 429.2304. Found: 429.2291. IR
(CHCl3) 1695, 1649, 1594, 1573 cm-1. 1H NMR (400 MHz, CDCl3) δ
0.70 (1H, m), 0.76-0.90 (2H, m), 1.19-1.36 (2H, m), 1.39-1.50 (1H,
m), 1.60 (3H, d, J ) 7.0 Hz), 1.60-1.72 (1H, m), 1.79-2.02 (3H, m),
2.13-2.32 (3H, m), 2.45 (1H, m), 2.71 (1H, m), 3.83 (1H, m), 5.00
(1H, dq, J ) 7.0, 7.0 Hz), 5.72 (1H, s), 6.75 (1H, m), 7.01-7.31 (8H,
m), 13.77 (1H, brs). 13C NMR (100 MHz, CDCl3) δ 24.9, 25.9, 27.2,
27.5, 28.9, 29.5, 29.9, 32.9, 33.3, 33.7, 54.9, 97.6, 108.9, 125.7, 125.8,
127.8, 127.9, 129.2, 129.4, 139.4, 140.2, 141.6, 163.9, 165.7, 176.6,
182.8. [R]24D -48.4 (c 1, CHCl3). CD (0.035 mM, CH3CN) 334.8 nm
(∆ꢀ ) +6.11), 271.8 (∆ꢀ ) -21.00), 225.8 (∆ꢀ ) +13.35), 214.0
(∆ꢀ ) -3.65).
(n ) 9): colorless oil. [R]24 -194.2 (c 1, CHCl3). CD (0.076 mM,
D
hexane) 325.6 nm (∆ꢀ ) -10.02), 254.6 (∆ꢀ ) +18.80), 232.4 (∆ꢀ )
-28.62), 215.8 (∆ꢀ ) +1.17). (S)-1 (n ) 9): colorless oil. [R]24
D
+186.6 (c 1, CHCl3). CD (0.074 mM, hexane) 324.4 nm (∆ꢀ ) +9.95),
255.2 (∆ꢀ ) -19.46), 232.6 (∆ꢀ ) +28.25), 216.4 (∆ꢀ ) -1.76).
(R)-1 (n ) 10): colorless needles of mp 54-56 °C (pentane). [R]23
D
-95.1 (c 1, CHCl3). CD (0.061 mM, hexane) 324.2 nm (∆ꢀ ) -6.33),
253.2 (∆ꢀ ) +17.71), 230.8 (∆ꢀ ) -15.12). (S)-1 (n ) 10): colorless
needles of mp 57-61 °C (pentane). [R]22 +95.1 (c 1, CHCl3). CD
D
(0.067 mM, hexane) 324.6 nm (∆ꢀ ) +7.46), 254.0 (∆ꢀ ) -18.43),
230.4 (∆ꢀ ) +17.30).
1,2-Bis[4-(2,2-dimethyl-4,6-dioxo-1,3-dioxan-5-yl)-5-oxopentyl]-
benzene, o-13. Under an argon atmosphere, a solution of 1,2-
benzenedipentanoic acid (0.60 g, 2.16 mmol) in SOCl2 (10 mL) was
refluxed for 3 h. After removal of SOCl2 in vacuo, the redisue was
diluted with dichloromethane (5 mL). The solution was then added
dropwise to a stirred solution of Meldrum’s acid (3, 0.60 g, 4.2 mmol)
and pyridine (1.58 g, 20 mmol) in dichloromethane (15 mL) under
ice-cooling over 15 min. The mixture was stirred for 30 min at the
temperature and then for 2 h at room temperature. After being acidified
with 10% hydrochloric acid, the organic materials were extracted with
chloroform. The organic layer was dried over MgSO4 and concentrated.
The residue was purified by column chromatography on neutral silica
gel using chloroform as an eluent giving o-13 (0.94 g, 82%) as yellowish
oil. MS (FAB) m/z 531 (M+ + 1). IR (CHCl3) 2940, 2865, 1740, 1665,
(R)- and (S)-o-15. A solution of (R,R)-imine (429 mg, 1.0 mmol)
and KOH (225 mg, 4.0 mmol) in THF (5 mL)-H2O (5 mL) was stirred
for 20 h at room temperature. The mixture was acidified with 10%
hydrochloric acid and then extracted with ether. The organic layer was
washed with brine, dried over MgSO4, and concentrated. The residue
was purified by column chromatography on neutral silica gel using
chloroform as an eluent to give (R)-o-15 (323 mg, 99%). Colorless
1
1576 cm-1. H NMR (400 MHz, CDCl3) δ 1.60-1.82 (8H, m), 1.73
(12H, s), 2.66 (4H, t, J ) 8.0 Hz), 3.13 (4H, t, J ) 8.0 Hz), 7.13 (4H,
s), 15.32 (2H, s). 13C NMR (100 MHz, CDCl3) δ 26.1, 26.9, 30.9,
32.3, 35.7, 91.3, 104.8, 126.0, 129.0, 139.4, 160.0, 170.3, 197.5.
1,2-Bis[4-(2,2-dimethyl-4-oxo-4H-1,3-dioxin-6-yl)butyl]ben-
zene, o-14. A solution of o-13 (940 mg, 1.77 mmol) and dry acetone
(0.5 mL, 6.80 mmol) in toluene (20 mL) was heated at reflux for 1 h.
After evaporation of the solvent, the residue was purified by silica gel
column chromatography using hexane/ethyl acetate (3:1) as an eluent
to give o-14 (400 mg, 51%) as colorless prisms. Mp 59-60 °C (ether).
Anal. calcd for C26H34O6: C, 70.56%; H, 7.74%. Found: C, 70.38%;
H, 7.85%. IR (CHCl3) 2999, 2940, 1730, 1632, 1490 cm-1. High-
resolution MS m/z calcd for C26H34O6 (M+): 442.2355. Found:
prisms of mp 100-102 °C (ether). [R]24 -107.4 (c 1, CHCl3). CD
D
(0.050 mM, CH3CN) 322.6 nm (∆ꢀ ) -12.95), 256.0 (∆ꢀ ) +25.96),
232.4 (∆ꢀ ) -28.93), 204.0 (∆ꢀ ) +9.47). (S)-o-15 was obtained
from (S,R)-imine in 92% yield. Colorless prisms of mp 103-105 °C
(ether). [R]24 +106.2 (c 1, CHCl3). CD (0.050 mM, CH3CN) 324.2
D
nm (∆ꢀ ) +14.30), 256.2 (∆ꢀ ) -29.51), 231.8 (∆ꢀ ) +32.00), 205.0
(∆ꢀ ) -12.71).
Cu[(R)-1 (n )8)]2, (R,R)-16 (n ) 8). Cu(OAc)2‚H2O (134 mg, 0.67
mmol) in 50% aqueous ethanol (2 mL) was added to (R)-1 (n ) 8)
(335 mg, 1.35 mmol) in 75% aqueous ethanol (10 mL), and the resulting
mixture was stirred at room temperature for 3 h. Then, the solvents
were evaporated in vacuo, and the residue was washed with water and
hexane. Recrystallization from chloroform-ether gave (R,R)-16 (n )
8) (364 mg, 98%). Blue prisms, mp >255 °C (dec). Anal. calcd for
C28H34CuO8: C, 59.83%; H, 6.10%. Found: C, 59.59%; H, 6.14%.
MS (FAB) m/z 561 for 63Cu[(R)-1 (n ) 8)]2, 563 for 65Cu[(R)-1 (n )
8)]2. IR (CHCl3) 3019, 2936, 1711, 1635, 1560 cm-1. [R]D24 +34.8 (c
0.1, CHCl3). UV (MeOH) λmax (ꢀ) 666 nm (70), 310 (24900), 244
(41500). CD (0.02 mM, MeOH) 683.2 nm (∆ꢀ ) -0.24), 322.0 (∆ꢀ
) -17.71), 274.0 (∆ꢀ ) +52.64), 241.4 (∆ꢀ ) -39.6).
1
442.2362. H NMR (400 MHz, CDCl3) δ 1.61-1.66 (8H, m), 1.67
(12H, s), 2.26 (4H, t, J ) 6.8 Hz), 2.62 (4H, t, J ) 7.2 Hz), 5.23 (2H,
s), 7.10-7.16 (4H, m). 13C NMR (100 MHz, CDCl3) δ 25.2, 25.8,
30.6, 32.4, 33.6, 93.3, 106.3, 126.1, 129.1, 139.3, 161.1, 171.4.
(()-7,8-Benzo-16-hydroxy-14-oxabicyclo[11.2.2]heptadecane-
1(16),7,13(17)-triene-2,15-dione, (()-o-15. To refluxing chlorobenzene
(500 mL) was added a solution of o-14 (1.23 g, 2.8 mmol) in
chlorobenzene (10 mL) dropwise by syringe pump over 24 h under an
argon atmosphere. After being heated at reflux for an additional 30
min, the solvent was evaporated in vacuo. The residue was purified by
column chromatography on neutral silica gel using chloroform as an
eluent giving (()-o-15 (0.77 g, 84%) as colorless prisms. Mp 95-96
°C (ether). Anal. calcd for C20H22O4: C, 73.60%; H, 6.79%. Found:
C, 73.78%; H, 6.87%. High-resolution MS m/z calcd for C20H22O4
(M+): 326.1518. Found: 326.1506. IR (CHCl3) 3019, 2938, 1730,
1635, 1556 cm-1. 1H NMR (400 MHz, CDCl3) δ 1.07 (1H, m), 1.38-
1.60 (3H, m), 1.73-2.10 (5H, m), 2.17-2.61 (5H, m), 2.85 (1H, dt, J
) 13.6, 4.4 Hz), 3.86 (1H, ddd, J ) 13.6, 8.0, 5.6 Hz), 5.98 (1H, s),
7.05-7.12 (4H, m), 15.46 (1H, br s). 13C NMR (100 MHz, CDCl3) δ
26.2, 27.4, 27.6, 30.1, 32.0, 32.7, 34.7, 38.2, 101.7, 102.4, 126.0, 126.1,
126.6, 130.0, 138.5, 140.4, 161.2, 172.4, 178.2, 207.7.
Cu[(R)-1 (n ) 9)]2, (R,R)-16 (n ) 9). Prepared from (R)-1 (n ) 9)
(132 mg, 0.50 mmol) and Cu(OAc)2‚H2O (49.9 mg, 0.25 mmol) in
94% yield (138 mg) as blue prisms. Mp 243-255 °C (dec) (acetone-
H2O). Anal. calcd for C30H38CuO8: C, 61.05%; H, 6.49%. Found: C,
60.90%; H, 6.51%. MS (FAB) m/z 589 for 63Cu[(R)-1 (n ) 9)]2, 591
for 65Cu[(R)-1 (n ) 9)]2. IR (CHCl3) 3019, 2932, 1713, 1637, 1556
24
cm-1. [R]D +29.8 (c 0.1, CHCl3). UV (MeOH) λmax (ꢀ) 656.0 (58),
303 (24300), 239 (43100). CD (0.02 mM, MeOH) 672.0 nm (∆ꢀ )
-0.25), 316.4 (∆ꢀ ) -17.2), 275.4 (∆ꢀ ) 50.2), 240.8 (∆ꢀ ) -46.3).
Cu[(R)-1 (n ) 10)]2, (R,R)-16 (n ) 10). Prepared from (R)-1 (n )
10) (214 mg, 0.77 mmol) and Cu(OAc)2•H2O (76.8 mg, 0.38 mmol)
in 96% yield (246 mg) as blue needles. Mp >255 °C (dec) (acetone-
H2O). Anal. calcd for C32H42CuO8: C, 62.17%; H, 6.65%. Found: C,
62.04%; H, 6.65%. MS (FAB) m/z 617 for 63Cu[(R)-1 (n ) 10)]2, 619
for 65Cu[(R)-1 (n ) 10)]2. IR (CHCl3) 3018, 2932, 1713, 1641, 1555
Imines of o-15. Under an argon atmosphere, a solution of (()-o-15
(32.6 mg, 0.10 mmol) and (R)-1-phenylethylamine (0.038 mL, 0.3
mmol) in benzene (15 mL) was heated at reflux for 1 h. After
evaporation of the solvent, the residue was purified by column
chromatography on neutral silica gel using hexane/ethyl acetate (4:1)
as an eluent to give first (R,R)-imine (20 mg, 47%) and then (S,R)-
imine (19 mg, 46%). (R,R)-Imine: colorless prisms of mp 124-126
cm-1. [R]D +49.8 (c 0.1, CHCl3). UV (MeOH) λmax (ꢀ) 654 (40),
24

8276 J. Am. Chem. Soc., Vol. 121, No. 36, 1999
Sato et al.
304 (28000), 238 (48700). CD (0.02 mM, MeOH) 671.0 nm (∆ꢀ )
-0.26), 315.8 (∆ꢀ ) -7.12), 274.2 (∆ꢀ ) +38.1), 238.8 (∆ꢀ ) -31.2).
Cu[(R,R)-6 (n ) 9)]2, (R,R,R,R)-17 (n ) 9). A solution of (R,R)-6
(141 mg, 0.40 mmol) and Et3N (0.058 mL, 0.4 mmol) in THF (2 mL)
was added to a stirred solution of copper (II) trifluoromethanesulfonate
(72.4 mg, 0.20 mmol) in THF (2 mL) under an argon atmosphere.
Stirring was continued at room temperature for 12 h and then at 50 °C
for 12 h. After evaporation of the solvent, the residue was washed with
water and dried in vacuo, giving the copper complex (157 mg, 99%)
as a dark blue amorphous solid. Mp 150-160 °C (dec). Anal. calcd
for C46H56CuN2O6: C; 69.37%, H; 7.09%, N; 3.52%. Found: C;
69.33%, H; 7.25%, N; 3.45%. MS (FAB) m/z 793 for 63Cu[(R,R)-6 (n
) 9)]2+1, 795 for 65Cu[(R,R)-6 (n ) 9)]2+1. IR (CH2Cl2) 1693, 1641,
Found: C, 57.92%; H, 6.48%. MS (FAB) m/z 982 for 151Eu[(R)-1 (n
) 10)]3, 984 for 153Eu[(R)-1 (n ) 10)]3. IR (CHCl3) 3020, 2931, 1677,
1646, 1587, 1421 cm-1. [R]D +125.2 (c 1, CHCl3). CD (0.012 mM,
24
MeOH) 310.2 nm (∆ꢀ ) -13.13), 261.6 (∆ꢀ ) +93.42), 241.4 (∆ꢀ )
-31.54), 223.4 (∆ꢀ ) +6.82).
X-ray Crystallography. Crystal data, data collection, and refinement
for the compounds of (R,R)-6 (n ) 10), (R,R)-16 (n ) 8), and (R,R)-
16 (n ) 9) are summarized in Table 2. X-ray diffraction measurements
were made on a Rigaku AFC5R diffractometer using graphite mono-
chromated Mo-KR radiation (λ )0.71069 Å). The latter two crystals
of Cu complex were coated with epoxy resins and treated at low
temperature (150 K). All data were corrected for Lorenz and polarization
effects, and the empirical ψ scan absorption correction was applied.
The structures were solved by direct methods and refined using full-
matrix least squares. All nonhydrogen atoms were refined anisotropi-
cally. At this stage, the difference Fourier map for the (R,R)-16 (n )
8) indicated that acetone molecules were included in the crystal, the
position of which was refined anisotropically. The acetone molecule
was included into a cavity formed by the two bridging methylenes (see
Figure 4). Large temperature factors suggest disorder or insufficient
content of the acetone molecule. Treatment of hydrogen atoms was
made on the basis of the peak appearance in the D-map. For (R,R)-6
(n ) 10), since no peaks appeared in geometrically reasonable positions,
positions for hydrogen atoms were calculated and fixed in the
refinement. For (R,R)-16 (n ) 8), about half of the hydrogen atoms
were found. The starting positions therefore were calculated, and the
damped refinement was applied to give some changes of the model.
Finally it was refined without damping, and hydrogen atoms were fixed.
For (R,R)-16 (n ) 9), since all positions were found from the D-map,
hydrogen atoms were refined in the normal way. The function
minimized in the refinement was Σw (|Fo| - |Fc|)2. The weighting
scheme was based on counting statistics and included a factor to
downweight the intense reflections (p factor). All calculations were
carried out using teXsan software package (Crystal Structure Analysis
Package, Molecular Structure Corporation, 1985 & 1992). Further
experimental details and tables of atomic coordinates, bond lengths,
and angles are given as Supporting Information, and also deposited
with Cambridge Crystallographic Data Center (CCDC, University
Chemical Laboratory, Lensfield Road, Cambridge CB21EW, U.K).
1572 cm-1. [R]24 -44 (c 0.05, CH2Cl2). UV (CH2Cl2) λmax (ꢀ) 558
D
nm (130), 324 (25900), 248 (21700). CD (0.02 mM, CH2Cl2) 700 nm
(∆ꢀ ) +0.50), 556.0 (∆ꢀ ) -2.09), 428.5 (∆ꢀ ) -0.36), 336.5 (∆ꢀ
) -9.71), 270.5 (∆ꢀ ) +55.16), 247.0 (∆ꢀ ) -18.0).
Cu[(S,R)-16 (n ) 9)]2, (S,R,S,R)-17 (n ) 9). Yield, 100%. Dark
green needles of mp 230-235 °C (dec) (dichloromethane-hexane).
Anal. calcd for C46H56CuN2O6: C, 69.37%; H, 7.09%; N, 3.52%.
63
Found: C, 69.29%; H, 7.14%; N, 3.48%. MS (FAB) m/z 793 for
-
Cu[(S,R)-16 (n ) 9)]2+1, 795 for 65Cu[(S,R)-16 (n ) 9)]2+1. IR (CH2-
Cl2) 1689, 1642, 1565 cm-1. [R]24 -396 (c 0.05, CH2Cl2). UV
D
(CH2Cl2) λmax (ꢀ) 642 nm (280), 326 (21200), 250 (12000). CD (0.02
mM, CH2Cl2) 752 nm (∆ꢀ ) -0.50), 597.0 (∆ꢀ ) +2.65), 437.0 (∆ꢀ
) +1.02), 307.5 (∆ꢀ ) -37.7), 278.5 (∆ꢀ ) -55.45).
Eu[(R)-1 (n )8)]3, (R,R,R)-18 (n ) 8). To (R)-1 (n ) 8) (150 mg,
0.60 mmol) in 50% aqueous ethanol (6 mL) was added 2 M KOH
(0.30 mL, 0.60 mmol), and the mixture was stirred for 0.5 h. Then,
EuCl3‚6H2O (73.2 mg, 0.20 mmol) was added. Stirring was continued
at room temperature for 1 day and then at 50 °C for 1 day. After
evaporation of the solvent, the residue was washed with water and
hexane, and dried in vacuo giving (R,R,R)-18 (n ) 8) (144 mg, 80%)
as colorless amorphous. Anal. calcd for C42H51EuO12: C, 56.06%; H,
5.71%. Found: C, 56.66%; H, 5.33%. MS (FAB) m/z 898 for 151Eu-
[(R)-1 (n )8)]3, 900 for 153Eu[(R)-1 (n )8)]3. IR (CHCl3) 3019, 2936,
1698, 1639, 1587, 1420 cm-1. [R]D24 +105.4 (c 1, CHCl3). CD (0.012
mM, MeOH) 312.8 nm (∆ꢀ ) -31.92), 262.8 (∆ꢀ ) +129.3), 245.2
(∆ꢀ ) -57.76), 225.6 (∆ꢀ ) +20.04).
Eu[(R)-1 (n )9)]3, (R,R,R)-18 (n ) 9). Prepared from (R)-1 (n )
9) (106 mg, 0.40 mmol) and EuCl3‚6H2O (48.7 mg, 0.13 mmol) in
98% yield (120 mg) as colorless amorphous. Anal. calcd for C45H57-
EuO12: C, 57.38%; H, 6.10%. Found: C, 57.35%; H, 6.10%. MS (FAB)
m/z 940 for 151Eu[(R)-1 (n )9)]3, 942 for 153Eu[(R)-1 (n ) 9)]3. IR
(CHCl3) 3020, 2930, 1683, 1642, 1586, 1423 cm-1. [R]D24 +72.0 (c 1,
CHCl3). CD (0.02 mM, MeOH) 310.2 nm (∆ꢀ ) -20.13), 262.8 (∆ꢀ
) +96.26), 243.0 (∆ꢀ ) -44.8), 224.2 (∆ꢀ ) +6.95).
Eu[(R)-1 (n )10)]3, (R,R,R)-18 (n ) 10). Obtained from (R)-1
(n ) 10) (83.4 mg, 0.30 mmol) and EuCl3‚6H2O (36.6 mg, 0.10 mmol)
in 90% yield (88.2 mg) as colorless needles. Mp 210-225 (dec)
(ethanol-H2O). Anal. calcd for C48H63EuO12: C, 58.59%; H, 6.45%.
Acknowledgment. This work was supported by grants from
the Japan Society for Promotion of Science (RFTF 97P00302).
Supporting Information Available: Synthetic procedures
and/or spectral data of 4 (n ) 6-12,16) and 7-15; tables of
atomic coordinates, bond lengths, and angles. The material is
found in libraries on microfiche. This material is available free
of charge via the Internet at http://pubs.acs.org.
JA983907U