Synthesis of concave 1,10-phenanthrolines by a combination of Suzuki coupling, ring closing metathesis and hydrogenation

Article abstract of DOI:10.1002/ejoc.200400068

A wide variety of saturated and unsaturated concave 1,10-phenanthrolines 2 and 4 have been synthesized in good yields starting from dichloro-1,10- phenanthroline 14. In the three step synthesis, Suzuki couplings of bis-ortho-substituted boronic acids were

Full text of DOI:10.1002/ejoc.200400068

FULL PAPER
Synthesis of Concave 1,10-Phenanthrolines by a Combination of Suzuki
Coupling, Ring Closing Metathesis and Hydrogenation[‡]
Ulrich Lüning*[a] and Frank Fahrenkrug[a]
Keywords: Cross-coupling / Cyclization / Macrocycles / Metathesis / Supramolecular chemistry
A wide variety of saturated and unsaturated concave 1,10-
phenanthrolines 2 and 4 have been synthesized in good
yields starting from dichloro-1,10-phenanthroline 14. In the
three step synthesis, Suzuki couplings of bis-ortho-substi-
of different lengths, underwent ring closing metathesis reac-
tions giving (bi)macrocyclic 1,10-phenanthrolines 4 in yields
between 73 and 96%. The alkene chains of 4 were saturated
using hydrogen and Pd/C giving the concave 1,10-phen-
tuted boronic acids were used to introduce two different or anthrolines 2 in yields between 75 and 99%.
two identical aryl bridgeheads into the 2- and 9-positions of
the 1,10-phenanthroline (yields Ն70%). The resulting diaryl-
1,10-phenanthrolines 3, substituted with alkenyloxy groups
( Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
Germany, 2004)
Introduction
Results and Discussion
2,9-Dihalo-1,10-phenanthrolines and areneboronic acids
are the building blocks for the construction of 2,9-disubsti-
tuted 1,10-phenanthrolines using the Suzuki coupling. Syn-
thesis of 2,9-dihalo-1,10-phenanthrolines is well estab-
lished,[23,24] and it has been shown that the reactivity of 2,9-
dichloro-1,10-phenanthroline (14) is sufficient for coupling
with areneboronic acids.[22]
The high selectivity of enzymes is largely a result of the
concave environment of the active site.[1] Therefore, also in
supramolecular chemistry,[2Ϫ5] geometrically related mol-
ecules such as macrocycles, clefts or pincers have attracted
wide interest. Concave reagents have been developed in or-
der to increase the selectivity of reactions or catalytic pro-
cesses by variation of the shielding of the reaction site. In
particular, the concave 1,10-phenanthrolines 2 have shown
good selectivities in a number of reactions.[6Ϫ10] In most of
these cases, transition metal ion complexes of the ligands
are active and selective catalysts. For example, copper()
complexes of the ligands catalyze the stereoselective cyclo-
propanation of alkenes by diazoacetates.[11Ϫ21]
We have shown that concave 1,10-phenanthrolines 2 can
be synthesized in good yields, not only starting from the
tetraphenol 1 (see Scheme 1), but also by a combination of
Suzuki coupling, ring closing metathesis and hydrogen-
ation.[14,22] In this way, a greater variety of concave 1,10-
phenanthrolines can be obtained than by the double cycli-
zation method, which uses a fourfold Williamson ether syn-
thesis (Scheme 1).[6] Here we report on the synthesis of both
unsymmetric bi- and mono-macrocyclic 1,10-phenanthrol-
ines.
In order to synthesize concave 1,10-phenanthrolines with
only one chain, or with two different chains X1 and X2 or
Y1 and Y2, respectively (see Scheme 5, below), it was
necessary to prepare the new boronic acids 8 and 13. Their
syntheses are summarized in Scheme 2 and Scheme 3.
The synthesis of both compounds is straightforward
starting from the bromo-substituted resorcinol 5.[25] Initial
etherification of the phenols was followed by introduction
of the boronic acid functionality. Unsymmetrical bis-ortho-
substitution of the boronic acids 8 and 13 was achieved by
a stepwise alkylation. In the preparation of the methoxy-
substituted boronic acid 8, no protecting group was used.
The first alkylating step was the mono-methylation of 5 in
51% yield followed by a hexenylation of the second OH
group in 94% yield. In the case of 13, one methoxymethyl
protecting group was introduced to 5 to give 9 in 31% yield,
followed by hexenylation of the second phenol group to give
10 in 97% yield. Following deprotection (89% yield), the
butenyl group of 12 was introduced by a Mitsunobu coup-
ling to avoid the problem of butadiene formation which is
known to occur during the butenylation of related phen-
ols.[22] The reaction of 11 with 3-butenol, triphenylphos-
phane, and diethyl azodicarboxylate gave the unsymmetri-
cally substituted phenol 12 in 64% yield.
[‡]
Concave Reagents, 41. Part 40: R. Cacciapaglia, S. Di Stefano,
F. Fahrenkrug, U. Lüning, L. Mandolini, J. Phys. Org. Chem.
2004, 17, 350Ϫ355.
[a]
Institut für Organische Chemie, Universität Kiel,
Olshausenstr. 40, 24098 Kiel, Germany
Fax: (internat.) ϩ 49-(0)431-880-1558
E-mail: luening@oc.uni-kiel.de
Eur. J. Org. Chem. 2004, 3119Ϫ3127
DOI: 10.1002/ejoc.200400068
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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U. Lüning, F. Fahrenkrug
FULL PAPER
Scheme 1
Scheme 2
The boronic acids were synthesized from the 2-bromodi-
ethers 7 and 12 by a bromine-lithium exchange followed
by reaction with trimethylborate. Aqueous workup gave the
boronic acids 8 and 13 in 57% and 78% yield, respectively.
As has been demonstrated for other boronic acids that
form the concave 1,10-phenanthrolines 3a؊c,[22] the bo-
ronic acids 8, 13 and 15[22] were then coupled with chloro-
substituted 1,10-phenanthrolines. A one-step reaction with
2,9-dichloro-1,10-phenanthroline (14) yielded the 2,9-di-
aryl-substituted 1,10-phenanthroline 3e with two identical
aromatic rings while a two-step reaction yielded initially the
mono-arylated intermediate 16 followed by the required
product 3d with two different aryl rings in the 2- and 9-
positions. When performed using Pd(PPh3)4 as catalyst, ba-
rium hydroxide as base and dimethoxyethane as solvent,
the Suzuki couplings gave yields of 92% (3e) and 78 and
76% (3d, first and second step) (Scheme 4).
Scheme 3
Thus, Suzuki couplings (see also ref.[22]) provided a num-
The RCM products 4 were mixtures of isomers (cis/trans-
ber of alkenyl-substituted diaryl-1,10-phenanthrolines 3, alkene) but simple hydrogenolyses in ethyl acetate using pal-
which were then subjected to ring closing metatheses ladium on charcoal and hydrogen transformed these into
(RCM) (see Scheme 5). In all cases, the macrocycles 4 were the macrocyclic 1,10-phenanthrolines 2 containing satu-
formed in good yields (73Ϫ96%), although the reactions rated chains, Y, in good yields. Considering 2aϪe, only a
were carried out in only moderately dilute solutions.
few of these macrocyclic 1,10-phenanthrolines were access-
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Eur. J. Org. Chem. 2004, 3119Ϫ3127

Synthesis of Concave 1,10-Phenanthrolines
FULL PAPER
Scheme 4
Scheme 5
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U. Lüning, F. Fahrenkrug
FULL PAPER
temp. After quenching with water (20 mL), the layers were sepa-
rated and the aqueous layer was extracted three times with diethyl
ether (20Ϫ30 mL). The combined organic fractions were washed
with brine (20Ϫ30 mL) and dried with magnesium sulfate. After
evaporation of the solvent, the crude product was purified as de-
tailed below.
ible by the double macrocyclization of the tetraphenol 1.
Thus, bimacrocycles containing identical chains Y1 and Y2,
with odd or even numbers of CH2 groups (2a؊c), a bimac-
rocycle with non-identical chains Y1 and Y2 (2d), and a
monomacrocycle 2e are all readily available using the pre-
sented methodology.
General Procedure for the Ring Closing Metathesis (RCM): The
1,10-phenanthroline 3 (di- or tetraene) was dissolved in dichloro-
methane (c ϭ 0.01 mmol/L). Benzylidene-bis(tricyclohexylphos-
phane)dichlororuthenium (5 mol %) was added and the mixture
was stirred for 16 h at room temp. After three filtrations through
basic alumina using dichloromethane, the resulting isomeric mix-
ture was analyzed. Melting points were not determined.
Some of these compounds have been tested already as
selectivity enhancing ligands in transition metal cata-
lyses,[7,10] e.g. in the cyclopropanation of alkenes. The use
of a proper concave ligand boosts the diastereoselectivity
of the cyclopropanation of, for instance, indene to 140:1
(exo/endo).
General Procedure for Hydrogenolysis of the Double Bonds of the
RCM Products: The RCM product was dissolved in ethyl acetate
(c ഠ 30 mmol/L). In a separate vessel, palladium on charcoal (10%)
(10.0 mg per 100 µmol of starting material) was suspended in ethyl
acetate (5.0 mL) and hydrogen was bubbled through the mixture
for 30 min to activate the catalyst. Subsequently, the RCM product
solution was added and hydrogen was bubbled through the mixture
for 2 h with stirring at room temp. With the mixture remaining in
a hydrogen atmosphere, stirring was continued for an additional
16 h at room temp. After evaporation of the solvent in vacuo, the
crude product was dissolved in dichloromethane, filtered through
basic alumina and recrystallized from dichloromethane/hexane.
Experimental Section
General Remarks: The following chemicals were obtained commer-
cially and used without further purification: N,N-dimethylformam-
ide (Fluka, 1, 99.8%), dimethyl sulfate (Merck), tetrakis(triphenyl-
phosphane)palladium(0) (Aldrich), dimethoxyethane (Aldrich), 3-
buten-1-ol (Fluka), 5-bromo-1-pentene (Fluka), 6-bromo-1-hexene
(Fluka), diethyl azodicarboxylate (Fluka), triphenylphosphane (Al-
drich), trimethyl borate (Fluka), n-butyllithium 2.5  solution
in hexanes (Aldrich), benzylidene-bis(tricyclohexylphosphanyl)di-
chlororuthenium (Fluka). 2-Bromo-1,3-dihydroxybenzene (5),[25] 2,6-
bis(hex-5-enyloxy)benzeneboronic acid (15)[22] and 2,9-dichloro-
1,10-phenanthroline (14)[24] were prepared according to literature
procedures. Dry solvents were obtained using suitable desiccants:
tetrahydrofuran was distilled from lithium aluminium hydride and
ethyl acetate was distilled from calcium chloride. Column chroma-
tography was carried out on basic alumina (Fluka, activity I) or
silica gel (MachereyϪNagel, activity I). The 1H NMR and 13C
NMR spectra were recorded on Bruker AC 200 (200 MHz), AM
300 (300 MHz or 75 MHz) or DRX 500 (500 MHz or 125 MHz)
spectrometers, using tetramethylsilane as internal standard. IR
spectra were measured on a PerkinϪElmer 1600 Series. MS spectra
were recorded on a Finnigan MAT 8230. Elemental analyses were
carried out on a VarioEl, Elementaranalysensysteme GmbH. Gas
2,11,13,22-Tetraoxa-1,12(1,3,2)-dibenzena-23(2,9)-1,10-phenanthro-
linabicyclo[10.10.1]tricosaphane (2a): Batch size: 200 mg
(326 mmol) of 4a. Yield 201 mg (99%), ref.[14] 99%. M.p. 242Ϫ243
°C, ref.[14] 249 °C. IR (KBr): ν˜ ϭ 3039 (arom. CϪH), 2929, 2854
(aliph. CϪH), 1594, 1457 (arom. CϭC), 1102 (CϪOϪC) cmϪ1. 1H
NMR (300 MHz, CDCl3): δ ϭ 0.74, 0.94, 1.38 (3 mc, 24 H, CH2),
3.77, 3.97 (2 mc, 8 H, OCH2), 7.23 (t, J ϭ 8.4 Hz, 4 H, 3Ј,3ЈЈ,5Ј,5ЈЈ-
H), 7.54 (d, J ϭ 8.4 Hz, 2 H, 4Ј,4ЈЈ-H), 7.54 (d, J ϭ 8.2 Hz, 2 H,
3,8-H), 7.82 (s, 2 H, 5,6-H), 8.22 (d, J ϭ 8.2 Hz, 2 H, 4,7-H) ppm.
MS (EI, 70 eV): m/z (%) ϭ 616 (100) [Mϩ], 573 (25) [Mϩ Ϫ C3H7],
531 (24) [Mϩ Ϫ C6H13].
2,12,14,24-Tetraoxa-1,13(1,3,2)-dibenzena-25(2,9)-1,10-phenanthro-
linabicyclo[11.11.1]pentacosaphane (2b): Batch size: 268 mg
(418 µmol) of 4b. Yield 268 mg (99%). M.p. 206Ϫ208 °C. IR (KBr):
ν˜ ϭ 3038 (arom. CϪH), 2927, 2855 (aliph. CϪH), 1592, 1457
chromatography was performed using
Chromatograph equipped with
MachereyϪNagel.
a
Varian 3400 Gas
a column SE30/25m from
(arom. CϭC), 1103 (CϪOϪC) cmϪ1
.
1H NMR (300 MHz,
General Procedure for the Williamson Synthesis of Aryl Alkenyl
Ethers (7, 10): The phenolic starting material was dissolved in dry
N,N-dimethylformamide. After addition of a catalytic amount of
potassium iodide and ca. three equivalents of potassium carbonate
per phenol function, the appropriate ω-bromo-1-alkene (1.25
equivalents) was added. After 16 h of stirring at 60 °C, the solvent
was removed in vacuo and 2  sodium hydroxide (20Ϫ30 mL) and
diethyl ether (20Ϫ30 mL) were added to the residue. The aqueous
layer was separated and extracted three times with diethyl ether
(20Ϫ30 mL). The combined organic fractions were washed three
times with 2  sodium hydroxide (20Ϫ30 mL) and once with brine
(20Ϫ30 mL). After drying with magnesium sulfate, the solvent was
evaporated in vacuo and the crude product purified by filtration
through silica gel after dissolving in the solvent indicated below.
CDCl3): δ ϭ 0.28, 0.71, 0.85, 1.42 (4 mc, 28 H, CH2), 3.77, 3.97
(2 mc, 8 H, OCH2), 5.30 (s, 1.8 H, CH2Cl2), 6.60 (d, J ϭ 8.3 Hz,
4 H, 3Ј,3ЈЈ,5Ј,5ЈЈ-H), 7.23 (t, J ϭ 8.3 Hz, 2 H, 4Ј,4ЈЈ-H), 7.58 (d,
J ϭ 8.2 Hz, 2 H, 3,8-H), 7.80 (s, 2 H, 5,6-H), 8.21 (d, J ϭ 8.2 Hz,
2 H, 4,7-H) ppm. 13C NMR (75 MHz, CDCl3): δ ϭ 24.8, 26.7,
28.4, 28.4 (4 t, CH2), 53.5 (t, CH2Cl2), 67.9 (t, OCH2), 105.8 (d,
3Ј,3ЈЈ,5Ј,5ЈЈ-C), 121.5 (s, 1Ј,1ЈЈ-C), 125.8, 126.0 (2 d, 3,5,6,8-C),
127.2 (s, 4a,4b-C), 129.4 (d, 4Ј,4ЈЈ-C), 135.0 (d, 4,7-C), 146.4 (s,
10a,10b-C), 155.6 (s, 2,9-C), 158.0 (s, 2Ј,2ЈЈ,6Ј,6ЈЈ-C) ppm. MS (EI,
70 eV): m/z (%) ϭ 644 (100) [Mϩ], 630 (12) [Mϩ Ϫ CH2], 601 (20)
[Mϩ Ϫ C3H7]. HR-MS Ϫ C42H48N2O4: found 644.36030, calcd.
644.36139 (δ ϭ 0.6 ppm); C4113CH48N2O4: found 645.36460, calcd.
645.36475 (δ ϭ 0.2 ppm). C42H48N2O4 (644.84): calcd. C 78.72,
H 6.92, N 4.37; C42H44N2O4·1.3CH2Cl2·1.0H2O (769.24): calcd. C
67.61, H 6.37, N 3.63; found C 67.55, H 6.63, N 3.54.
General Procedure for the Synthesis of the Boronic Acids (8, 13):
The aryl bromide was dissolved in tetrahydrofuran then cooled to
Ϫ78 °C. n-Butyl lithium (1.1 equivalents, 2.5  in hexane) was ad-
ded and the mixture stirred for 1 h at Ϫ78 °C. After addition of
2,13,15,26-Tetraoxa-1,14(1,3,2)-dibenzena-27(2,9)-1,10-phenanthro-
linabicyclo[12.12.1]heptacosaphane (2c): Batch size: 109 mg
(162 µmol) of 4c. Yield 103 mg (95%), ref.[14] 95%. M.p. 182Ϫ183
ca. 3.3 equivalents of trimethylborate, stirring was continued for °C, ref.[14] 186 °C. IR (KBr): ν˜ ϭ 2924, 2852 (aliph. CϪH), 1595,
2 h. During this period, the mixture was allowed to warm to room
1456 (arom. CϭC), 1101 (CϪOϪC). 1H NMR (300 MHz, CDCl3):
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Synthesis of Concave 1,10-Phenanthrolines
FULL PAPER
δ ϭ 0.54, 0.65Ϫ0.98, 1.41 (mc, m, mc, 32 H, CH2), 3.84 (mc, 8 H, 1639, 1619 (aliph. CϭC), 1595, 1458 (arom. CϭC), 1105
OCH2), 6.59 (t, J ϭ 8.3 Hz, 4 H, 3Ј,3ЈЈ,5Ј,5ЈЈ-H), 7.23 (d, J ϭ (CϪOϪC) cmϪ1. 1H NMR (300 MHz, CDCl3): δ ϭ 1.19 (mc, 6 H,
8.3 Hz, 2 H, 4Ј,4ЈЈ-H), 7.57 (d, J ϭ 7.5 Hz, 2 H, 3,8-H), 7.81 (s,
2 H, 5,6-H), 8.21 (d, J ϭ 7.5 Hz, 2 H, 4,7-H) ppm. MS (EI, 70 eV):
O(CH2)2CH2CH2CHϭ), 1.48 [mc, 6 H, OCH2CH2(CH2)2CHϭ],
1.79 [mc, 6 H, O(CH2)3CH2CHϭ], 2.25 (tq, Jt ഠ 1, Jq ഠ 7 Hz,
2 H, OCH2CH2CHϭ), 3.90, 3.91 [2 t, J ϭ 6.4, J ϭ 6.4 Hz, 6 H,
m/z (%) ϭ 672 (100) [Mϩ], 629 (15) [Mϩ Ϫ C3H7], 615 (7) [Mϩ
Ϫ
C4H9], 601 (7) [Mϩ Ϫ C5H11], 587 (4) [Mϩ Ϫ C6H13], 559 (24) [Mϩ OCH2(CH2)3CHϭ], 3.99 (t, J ϭ 6.8 Hz, 2 H, OCH2CH2CHϭ),
Ϫ C8H17].
4.7Ϫ4.9 (m, 8 H, ϭCH2), 5.4Ϫ5.7 (m, 4 H, CHϭ), 6.61 (d, J ϭ
8.4 Hz, 2 H, 3ЈЈ,5ЈЈ-H), 6.61 (mc, 2 H, 3Ј,5Ј-H), 7.24, 7.24 (2 t, J ϭ
8.4, J ϭ 8.4 Hz, 2 H, 4Ј,4ЈЈ-H), 7.59, 7.61 (2 d, J ϭ 8.2, J ϭ 8.2 Hz,
2 H, 3,8-H), 7.80 (s, 2 H, 5,6-H), 8.19, 8.19 (2 d, J ϭ 8.2, J ϭ
8.2 Hz, 2 H, 4,7-H) ppm. 13C NMR (75 MHz, CDCl3): δ ϭ 25.0,
25.1 [2 t, O(CH2)2CH2CH2CHϭ], 28.4, 28.4 (2 t, OCH2CH2CHϭ
), 33.1, 33.1 [2 t, OCH2CH2(CH2)2CHϭ], 33.6 (t, OCH2CH2CHϭ
), 68.8, 68.8 (2 t, OCH2), 106.1 (d, 3ЈЈ,5ЈЈ-C), 106.2, 106.6 (2 d,
3Ј,5Ј-C), 114.1, 114.2 [2 t, O(CH2)4CHϭCH2], 116.3 [t,
O(CH2)2CHϭCH2], 121.7, 121.7 (2 s, 1Ј,1ЈЈ-C), 125.8, 126.0 (2 d,
3,5,6,8-C), 127.2, 127.3 (2 s, 4a,6a-C), 129.4, 129.4 (2 d, 4Ј,4ЈЈ-C),
134.7, 134.8, 138.6 (3 d, 4,7-C, CHϭ), 146.3, 146.4 (2 s, 10a,10b-
C), 154.9, 155.1 (2 s, 2,9-C), 157.9, 158.0, 158.0 (3 s, 2Ј,2ЈЈ,6Ј,6ЈЈ-
C) ppm. MS (EI, 70 eV): m/z (%) ϭ 696 (100) [Mϩ], 655 (26) [Mϩ
Ϫ C3H5], 641 (40) [Mϩ Ϫ C4H7], 613 (55) [Mϩ Ϫ C6H11]. HR-MS
Ϫ C46H52N2O4: found 696.39240, calcd. 696.39270 (δ ϭ 0.4 ppm);
C4513CH52N2O4: found 697.39590, calcd. 697.39606 (δ ϭ 0.2 ppm).
C46H52N2O4 (696.93): calcd. C 79.28, H 7.52, N 4.02; found C
78.98, H 7.65, N 3.77.
2,11,13,24-Tetraoxa-1,12(1,3,2)-dibenzena-25(2,9)-1,10-phenanthro-
linabicyclo[12.10.1]pentacosaphane (2d): Batch size: 178 mg
(278 µmol) of 4d. Yield 135 mg (75%). M.p. 210Ϫ212 °C. IR (KBr):
ν˜ ϭ 3032 (arom. CϪH), 2924, 2860 (aliph. CϪH), 1602, 1486
(arom. CϭC), 1098 (CϪOϪC) cmϪ1
.
1H NMR (300 MHz,
CDCl3): δ ϭ 0.48, 0.78, 0.87, 0.97, 1.40 (5 mc, 28 H, CH2), 3.87
(mc, 8 H, OCH2), 5.29 (s, 0.11 H, CH2Cl2), 6.61 (mc, 4 H,
3Ј,3ЈЈ,5Ј,5ЈЈ-H), 7.25 (t, J ϭ 8.3 Hz, 2 H, 4Ј,4ЈЈ-H), 7.59 (d, J ϭ
8.2 Hz, 2 H, 3,8-H), 7.81 (s, 2 H, 5,6-H), 8.22 (d, J ϭ 8.2 Hz, 2 H,
4,7-H) ppm. 13C NMR (75 MHz, CDCl3): δ ϭ 24Ϫ29 (16 t, CH2),
67.9, 68.9, 68.9, 69.1 (4 t, OCH2), 105.5, 105.6, 105.8, 105.9 (4 d,
3Ј,3ЈЈ,5Ј,5ЈЈ-C), 120.8 (s, 1Ј,1ЈЈ-C), 126.0, 126.0 (2 d, 3,5,6,8-C),
127.2 (s, 4a,6a-C), 129.6 (d, 4Ј,4ЈЈ-C), 135.0 (d, 4,7-C), 146.0 (s,
10a,10b-C), 155.4 (s, 2,9-C), 157.9, 158.1 (2 s, 2Ј,2ЈЈ,6Ј,6ЈЈ-C) ppm.
MS (EI, 70 eV): m/z (%)
ϭ Ϫ
644 (100) [Mϩ]. HR-MS
C42H48N2O4: found 644.36100, calcd. 644.36139 (δ ϭ 0.6 ppm);
C4113CH48N2O4: found 645.36460, calcd. 645.36475 (δ ϭ 0.2 ppm).
C42H48N2O4 (644.84): calcd.
C
78.23,
H 7.50, N 4.34.
C42H48N2O4·0.1CH2Cl2·0.8H2O (667.72): calcd. C 75.73, H 7.52,
2,9-Bis[2-methoxy-6-(pent-4-enyloxy)phenyl]-1,10-phenanthroline
(3e): 2,9-Dichloro-1,10-phenanthroline (14, 214 mg, 968 µmol) was
dissolved in a mixture of dimethoxyethane (40 mL) and water
(10 mL). After addition of 2-methoxy-6-(pent-4-enyloxy)benzene-
boronic acid (8, 571 mg 2.42 mmol), barium hydroxide (622 mg,
N 4.20; found C 76.00, H 7.88, N 3.73.[26]
13,33-Dimethoxy-4,13-dioxa-1,3(1,2)-dibenzena-2(2,9)-1,10-phen-
anthrolinacyclotridecaphane (2e): Batch size: 235 mg (441 µmol) of
4e. Yield 234 mg (99%). M.p. 248 °C. IR (KBr): ν˜ ϭ 2927, 2825
(aliph. CϪH), 1595, 1462 (arom. CϭC), 1103 (CϪOϪC) cmϪ1. 1H
NMR (300 MHz, CDCl3): δ ϭ 0.70, 0.88, 1.35 (3 mc, 12 H, CH2),
3.70 (s, 6 H, OCH3), 3.87 (mc, 4 H, OCH2), 6.62 (mc, 4 H,
3Ј,3ЈЈ,5Ј,5ЈЈ-H), 7.28 (t, J ϭ 8.4 Hz, 2 H, 4Ј,4ЈЈ-H), 7.57 (d, J ϭ
8.3 Hz, 2 H, 3,8-H), 7.81 (s, 2 H, 5,6-H), 8.23 (d, J ϭ 8.3 Hz, 2 H,
4,7-H) ppm. 13C NMR (75 MHz, CDCl3): δ ϭ 25.6, 28.4, 28.8 (3 t,
CH2), 55.9 (q, OCH3), 69.1 (t, OCH2), 104.3, 105.9 (2 d,
3Ј,3ЈЈ,5Ј,5ЈЈ-C), 120.5 (s, 1Ј,1ЈЈ-C), 125.9, 126.2 (2 d, 3,5,6,8-C),
127.5 (s, 4a,6a-C), 129.7 (d, 4Ј,4ЈЈ-C), 135.4 (d, 4,7-C), 146.2 (s,
10a,10b-C), 155.4 (s, 2,9-C), 158.1, 158.2 (2 s, 2Ј,2ЈЈ,6Ј,6ЈЈ-C) ppm.
MS (EI, 70 eV): m/z (%) ϭ 534 (100) [Mϩ], 503 (19) [Mϩ Ϫ OCH3].
HR-MS Ϫ C34H34N2O4: found 534.25140, calcd. 534.25183 (δ ϭ
0.8 ppm); C3313CH34N2O4: found 535.25500, calcd. 535.25519 (δ ϭ
0.4 ppm). C34H34N2O4 (534.65), calcd. C 76.38, H 6.41, N 5.24.
C34H34N2O4·1.3H2O (558.06): calcd. C 73.18, H 6.61, N 5.02;
found C 73.08, H 6.87, N 4.77.
3.63 mmol)
and
tetrakis(triphenylphosphane)palladium(0)
(112 mg, 96.9 µmol), the mixture was heated at reflux for 16 h.
Then, water (20 mL) and dichloromethane (20 mL) were added and
the layers separated. The aqueous layer was extracted three times
with dichloromethane (20 mL), and the combined organic fractions
were washed with brine (20 mL) and dried with magnesium sulfate.
After evaporation of the solvent in vacuo, the crude product was
dissolved in dichloromethane, filtered through basic alumina and
recrystallized from dichloromethane/hexane. Yield 497 mg (92%).
M.p. 153 °C. IR (KBr): ν˜ ϭ 2941 (aliph. CϪH), 1638 (aliph. Cϭ
C), 1591, 1465 (arom. CϭC), 1104 (CϪOϪC) cmϪ1 1H NMR
.
(300 MHz, CDCl3): δ ϭ 1.58 (mc, 4 H, OCH2CH2), 1.88 (mc, 4 H,
CH2CHϭ), 3.72 (s, 6 H, OCH3), 3.90 (t, J ϭ 6.3 Hz, 4 H, OCH2),
4.70Ϫ4.85 (m, 4 H, ϭCH2), 5.59 (tdd, Jt ϭ 6.7, Jd ϭ 10.3, Jd ϭ
17.0 Hz, 2 H, CHϭ), 6.63, 6.63 (2 t, J ϭ 8.4, J ϭ 8.4 Hz, 4 H,
3Ј,3ЈЈ,5Ј,5ЈЈ-H), 7.27 (t, J ϭ 8.4 Hz, 1 H, 4Ј,4ЈЈ-H), 7.62 (d, J ϭ
8.2 Hz, 2 H, 3,8-H), 7.80 (s, 2 H, 5,6-H), 8.22 (d, J ϭ 8.2 Hz, 2 H,
4,7-H) ppm. 13C NMR (75 MHz, CDCl3): δ ϭ 28.2 (t, OCH2CH2),
29.9 (t, CH2CHϭ), 56.3 (q, OCH3), 67.9 (t, OCH2), 104.9, 105.6
(2 d, 3Ј,3ЈЈ,5Ј,5ЈЈ-C), 114.7 (t, ϭCH2), 120.6 (s, 1Ј,1ЈЈ-C), 126.0,
126.2 (2 d, 3,5,6,8-C), 127.4 (s, 4a,6a-C), 129.7 (d, 4Ј,4ЈЈ-C), 135.2
(d, 4,7-C), 138.0 (d, CHϭ), 146.2 (s, 10a,10b-C), 155.0 (s, 2,9-C),
157.8, 158.4 (2 d, 2Ј,2ЈЈ,6Ј,6ЈЈ-C) ppm. MS (EI, 70 eV): m/z (%) ϭ
560 (100) [Mϩ], 519 (90) [Mϩ Ϫ C3H5], 505 (63) [Mϩ Ϫ C4H7].
HR-MS Ϫ C36H36N2O4: found 560.26740, calcd. 560.26752 (δ ϭ
0.2 ppm); C3513CH36N2O4: found 561.27080, calcd. 561.27087 (δ ϭ
0.1 ppm). C36H36N2O4 (560.68): calcd. C 77.12, H 6.47, N 5.00;
C36H36N2O4·0.7H2O (573.29): calcd. C 75.19, H 6.59, N 4.87;
found C 75.15, H 6.87, N 4.73.
2-[2,6-Bis(hex-5-enyloxy)phenyl]-9-[2-(but-3-enyloxy)-6-(hex-5-
enyloxy)phenyl]-1,10-phenanthroline (3d): 2-[2,6-Bis(hex-5-enyloxy)-
phenyl]-9-chloro-1,10-phenanthroline (16, 500 mg, 1.03 mmol) was
dissolved in dimethoxyethane (60 mL) and water (15 mL), then 2-
(but-3-enyloxy)-6-(hex-5-enyloxy)benzeneboronic acid (13, 374 mg,
1.29 mmol), tetrakis(triphenylphosphane)palladium(0) (119 mg,
103µmol) and barium hydroxide (332 mg, 1.94 mmol) were added.
The mixture was heated at reflux for 16 h, allowed to cool, and
water (30 mL) and dichloromethane (30 mL) were added. The lay-
ers were separated and the aqueous layer was extracted three times
with dichloromethane (30 mL). The combined organic fractions
were washed with brine (20 mL) and dried over magnesium sulfate.
After evaporation to dryness, the crude product was dissolved in
dichloromethane, filtered through basic alumina and recrystallized
from dichloromethane/hexane. Yield 547 mg (76%). M.p. 82Ϫ85
°C. IR (KBr): ν˜ ϭ 3073 (arom. CϪH), 2935, 2868 (aliph. CϪH),
2,11,13,22-Tetraoxa-1,12(1,3,2)-dibenzena-23(2,9)-1,10-phenanthro-
linabicyclo[10.10.1]tricosaphan-6,17-diene (4a): Batch size: 200 mg
(299 µmol) of tetraene 3a. Yield 134 mg (73%), ref.[14] 73%. IR
Eur. J. Org. Chem. 2004, 3119Ϫ3127
www.eurjoc.org
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
3123

U. Lüning, F. Fahrenkrug
(KBr): ν˜ ϭ 2922 (aliph. CϪH), 1596, 1581 (arom. CϭC), 1246, 122.0 (s, 1Ј,1ЈЈ-C), 124.7, 125.1 (2 d, 3,5,6,8-C), 126.4 (s, 4a,6a-C),
FULL PAPER
1
1091 (CϪOϪC) cmϪ1. H NMR (300 MHz, CDCl3): δ ϭ 1.3Ϫ1.8
128.5 (d, 4Ј,4ЈЈ-C), 129.4 (d, CHϭCH), 134.7 (d, 4,7-C), 145.6 (s,
(m, 16 H, CH2), 3.8Ϫ4.2, 4.15 (m, mc, 8 H, OCH2), 4.66 (mc, 2.1 H, 10a,10b-C), 154.7 (s, 2,9-C), 157.2 (s, 2Ј,2ЈЈ,6Ј,6ЈЈ-C) ppm. MS (EI,
trans-CHϭCH), 4.99 (mc, 1.9 H, cis-CHϭCH), 5.30 (s, 0.26 H, 70 eV): m/z (%) ϭ 668 (51) [Mϩ], 640 (100) [Mϩ Ϫ C2H4], 627 (25)
CH2Cl2), 6.6Ϫ6.7 (m, 4 H, 3Ј,3ЈЈ,5Ј,5ЈЈ-H), 7.2Ϫ7.3 (m with t at
7.25, J ϭ 8.3 Hz and t at 7.24, J ϭ 8.3 Hz, 2 H, 4Ј,4ЈЈ-H), 7.60, found 668.36120, calcd. 668.36139 (δ ϭ 0.3 ppm); C4313CH48N2O4:
7.65 (2 d, J ϭ 8.2, J ϭ 8.2 Hz, 2 H, 3,8-H), 7.82, 7.83 (2 s, 2 H, found 669.36440, calcd. 669.36475 (δ ϭ 0.5 ppm). C44H48N2O4
[Mϩ Ϫ C3H5], 597 (62) [Mϩ Ϫ C5H11]. HR-MS Ϫ C44H48N2O4:
5,6-H), 8.22, 8.33 (2 d, J ϭ 8.2, J ϭ 8.2 Hz, 2 H, 4,7-H) ppm. cis/ (668.86): calcd. C 79.01, H 7.23, N 4.19; C44H48N2O4·0.4CH2Cl2
trans-ratio: 1:1.1. 13C NMR (125 MHz, CDCl3): δ ϭ 23.2, 28.9, (702.84): calcd. C 75.88, H 7.00, N 3.99; found C 75.74, H 7.17,
29.1, 29.4 (4 t, CH2), 54.2 (t, CH2Cl2), 69.4, 69.8 (2 t, OCH2), N 3.69. Using a chromatotron with neutral aluminium oxide and
107.9, 108.0 (2 d, 3Ј,3ЈЈ,5Ј,5ЈЈ-C), 123.0 (s, 1Ј,1ЈЈ-C), 125.9, 126.1
(2 d, 3,5,6,8-C), 127.0 (s, 4a,6a-C), 129.4, 129.6 (2 d, 4Ј,4ЈЈ-C, CHϭ
dichloromethane/pentane (1:1) as eluent, the isomer with a reson-
ance at δ ϭ 4.73 ppm could be separated from the mixture. 1H
CH), 134.7 (d, 4,7-C), 146.0 (s, 10a,10b-C), 155.0 (s, 2,9-C), 158.1, NMR (500 MHz, CDCl3): δ ϭ 1.03, 1.25, 1.3Ϫ1.5, 1.60 (2 mc, m,
158.1 (2 s, 2Ј,2ЈЈ,6Ј,6ЈЈ-C) ppm. MS (EI, 70 eV): m/z (%) ϭ 612 mc, 24 H, CH2), 3.81, 3.88 (2 mc, 8 H, OCH2), 4.73 (mc, 4 H, trans-
(100) [Mϩ], 530 (19) [Mϩ Ϫ C6H10], 396 (6) [C24H16N2O4]. HR- CHϭCH), 6.58 (d, J ϭ 8.4 Hz, 4 H, 3Ј,3ЈЈ,5Ј,5ЈЈ-H), 7.22 (t, J ϭ
MS Ϫ C40H40N2O4: found 612.29900, calcd. 612.29883 (δ ϭ
8.4 Hz, 2 H, 4Ј,4ЈЈ-H), 7.56 (d, J ϭ 8.1 Hz, 2 H, 3,8-H), 7.83 (s,
Ϫ0.3 ppm); C3913CH40N2O4: found 613.30200, calcd. 613.30219 2 H, 5,6-H), 8.23 (d, J ϭ 8.1 Hz, 2 H, 4,7-H). 1H NMR of the
(δ ϭ 0.3 ppm). C40H40N2O4 (612.77): calcd. C 78.41, H 6.58, N mixture, selected signals (500 MHz, CDCl3): δ ϭ 4.44 (mc, 0.62 H,
4.57; C40H40N2O4·0.1CH2Cl2 (621.25): calcd. C 77.53, H 6.52, N cis-CHϭCH), 4.73 (mc, 3.38 H, trans-CHϭCH), 8.2Ϫ8.3 (m, with
4.51; found C 77.55, H 6.83, N 4.57. Using a chromatotron with
neutral aluminium oxide and dichloromethane/pentane (1:1) as elu-
ent, the isomer with a resonance at δ ϭ 4.66 ppm could be sepa-
rated from the mixture. 1H NMR (500 MHz, CDCl3): δ ϭ 0.8Ϫ1.3,
1.44, 1.5Ϫ1.8 (m, mc, m, 16 H, CH2), 3.81, 3.91 (2 mc, 8 H, OCH2),
4.66 (mc, 4 H, ϭCH), 6.58 (d, J ϭ 8.3 Hz, 4 H, 3Ј,3ЈЈ,5Ј,5ЈЈ-H),
7.19 (t, J ϭ 8.3 Hz, 2 H, 4Ј,4ЈЈ-H), 7.60 (d, J ϭ 8.2 Hz, 2 H, 3,8-
H), 7.83 (s, 2 H, 5,6-H), 8.23 (d, J ϭ 8.2 Hz, 2 H, 4,7-H) ppm.
d at 8.22, J ϭ 8.1 Hz, 2 H, 4,7-H). cis/trans-ratio: 1:5.5.
2,11,13,24-Tetraoxa-1,12(1,3,2)-dibenzena-25(2,9)-1,10-phenanthro-
linabicyclo[12.10.1]pentacosaphan-5,18-diene (4d): Batch size:
400 mg (574 µmol) of tetraene 3d. Yield 303 mg (82%). IR (KBr):
ν˜ ϭ 2932 (aliph. CϪH), 1642 (aliph. CϭC), 1595, 1457 (arom. Cϭ
C), 1104 (CϪOϪC) cmϪ1 1H NMR (300 MHz, CDCl3): δ ϭ
.
0.8Ϫ1.2, 1.43, 2.09 (m with 2 mc at 0.85 and 1.04, 2 mc, 24 H, CH2),
3.82, 3.90 (2 mc, 8 H, OCH2), 4.42, 4.70, 5.04 (3 mc, 4 H, CHϭ
CH), 5.30 (s, 1.75 H, CH2Cl2), 6.5Ϫ6.7 (m, 4 H, 3Ј,3ЈЈ,5Ј,5ЈЈ-H),
7.21 (mc, 2 H, 4Ј,4ЈЈ-H), 7.48Ϫ7.65 (m, 2 H, 3,8-H), 7.76Ϫ7.82 (m
with s at 7.78, 2 H, 5,6-H), 8.18Ϫ8.24 (mc with d at 8.20, J ϭ
2,12,14,24-Tetraoxa-1,13(1,3,2)-dibenzena-25(2,9)-1,10-phenanthro-
linabicyclo[11.11.1]pentacosaphan-6,19-diene (4b): Batch size:
350 mg (502 µmol) of tetraene 3b. Yield 308 mg (96%). IR (KBr):
ν˜ ϭ 2927, 2866 (aliph. CϪH), 1594, 1456 (arom. CϭC), 1102 8.2 Hz, 2 H, 4,7-H) ppm. 13C NMR (75 MHz, CDCl3): δ ϭ 25Ϫ32
(CϪOϪC) cmϪ1. 1H NMR (300 MHz, CDCl3): δ ϭ 0.8Ϫ1.3, 1.44,
1.63 (m, 2 mc, 20 H, CH2), 3.6Ϫ4.1 (m, 8 H, OCH2), 4.3Ϫ4.5, 3Ј,3ЈЈ,5Ј,5ЈЈ-C), 121.3, 121.4 (2 s, 1Ј,1ЈЈ-C), 125Ϫ136 (16 signals,
4.8Ϫ5.0 (2 m, 1.3 H, 2.7 H, CHϭCH), 5.30 (s, 1.64 H, CH2Cl2), 4Ј,4ЈЈ3,4,4a,5,6,6a,7,8-C, CHϭCH), 146.5, 146.6 (2 s, 10a,10b-C),
(17 t, CH2), 53.5 (t, CH2Cl2), 68Ϫ70 (5 t, OCH2), 104Ϫ107 (6 d,
6.5Ϫ6.6 (m, 4 H, 3Ј,3ЈЈ,5Ј,5ЈЈ-H), 7.23 (mc, 2 H, 4Ј,4ЈЈ-H), 7.63 (mc, 155.7, 155.8 (2 s, 2,9-C), 158Ϫ159 (4 s, 2Ј,2ЈЈ,6Ј,6ЈЈ-C) ppm. MS
2 H, 3,8-H), 7.80, 7.80, 7.81 (3 s, 2 H, 5,6-H), 8.19 (mc, 2 H, 4,7-
(EI, 70 eV): m/z (%) ϭ 640 (100) [Mϩ], 612 (77) [Mϩ Ϫ C2H4],
569 (43) [Mϩ Ϫ C5H11]. HR-MS Ϫ C42H44N2O4: found 640.32970,
H) ppm. Isomer ratio (cis and trans not assignable): 1:2. 13C NMR
(75 MHz, CDCl3): δ ϭ 23Ϫ32 (16 t, CH2), 53.6 (s, CH2Cl2), 66Ϫ70 calcd. 640.33008 (δ ϭ 0.4 ppm); C4113CH44N2O4: found 641.33360,
(8 t, OCH2), 105Ϫ108 (6 d, 3Ј,3ЈЈ,5Ј,5ЈЈ-C), 120Ϫ123 (4 s, 1Ј,1ЈЈ-C),
calcd. 641.33344 (δ ϭ Ϫ0.3 ppm). C42H44N2O4 (640.81): calcd. C
125Ϫ132 (15 signals, 4Ј,4ЈЈ,3,4a,5,6,6a,8-C), 134.9, 134.9, 135.1 78.72, H 6.92, N 4.37; C42H44N2O4·0.9CH2Cl2 (717.25): calcd. C
(3 d, 4,7-C, CHϭCH), 145Ϫ148 (4 s, 10a,10b-C), 155.3, 155.4, 71.84, H 6.44, N 3.92; found C 71.63, H 6.33, N 3.79.
155.6 (3 s, 2,9-C), 157Ϫ159 (5 s, 2Ј,2ЈЈ,6Ј,6ЈЈ-C) ppm. MS (EI,
13,33-Dimethoxy-4,13-dioxa-1,3(1,2)-dibenzena-2(2,9)-1,10-phen-
anthrolinacyclotridecaphan-8-ene (4e): Batch size: 400 mg
(713 µmol) of diene 3e. Yield 360 mg (95%). IR (KBr): ν˜ ϭ 2925,
2869, 2840 (aliph. CϪH), 1595, 1461 (arom. CϭC), 1104
70 eV): m/z (%) ϭ 640 (100) [Mϩ], 612 (44) [Mϩ Ϫ C2H4], 569 (18)
[Mϩ Ϫ C5H11]. HR-MS Ϫ C42H44N2O4: found 640.32970, calcd.
640.33008 (δ ϭ 0.6 ppm); C4113CH44N2O4: found 641.33360, calcd.
641.33344 (δ ϭ Ϫ0.3 ppm). C42H44N2O4 (640.81): calcd. C 78.72,
H 6.92, N 4.37; C42H44N2O4·0.8CH2Cl2 (708.76): calcd. C 72.53,
H 6.48, N 3.95; found C 72.88, H 6.92, N 3.76.
1
(CϪOϪC) cmϪ1. H NMR (300 MHz, CDCl3): δ ϭ 0.89, 1.2Ϫ1.7
(mc, m, 8 H, CH2), 3.67, 3.70 (2 s, 6 H, OCH3), 3.88, 3.95 (2 mc,
4 H, OCH2), 4.68 (mc, 1.15 H, trans-CHϭCH), 5.04 (mc, 0.85 H,
2,13,15,26-Tetraoxa-1,14(1,3,2)-dibenzena-27(2,9)-1,10-phen- cis-CHϭCH), 6.61Ϫ6.68 (m, 4 H, 3Ј,3ЈЈ,5Ј,5ЈЈ-H), 7.27, 7.27 (2 t,
anthrolinabicyclo[12.12.1]heptacosaphan-7,20-diene (4c): Batch
size: 250 mg (349 µmol) of tetraene 3c. Yield 215 mg (321 µmol)
J ϭ 8.3, J ϭ 8.3 Hz, 2 H, 4Ј,4ЈЈ-H), 7.58, 7.62 (2 d, J ϭ 8.2, J ϭ
8.2 Hz, 2 H, 3,8-H), 7.80, 7.80 (2 s, 2 H, 5,6-H), 8.22, 8.23 (2 d, J ϭ
(92%), ref.[14] 92%. IR (KBr): ν˜ ϭ 2925 (aliph. CϪH), 1595 (arom. 8.2, J ϭ 8.2 Hz, 2 H, 4,7-H) ppm. cis/trans-ratio: 1:1.3. 13C NMR
1
CϭC), 1103 (CϪOϪC) cmϪ1. H NMR (300 MHz, CDCl3): δ ϭ (75 MHz, CDCl3): δ ϭ 23.0, 28.9, 29.1, 29.4 (4 t, CH2), 55.7, 55.9
0.9Ϫ1.7, 1.05, 1.35, 1.55 (m, 3 mc, 24 H, CH2), 3.84 (mc, 8 H, (2 q, OCH3), 68.4, 69.6 (2 t, OCH2), 104.4, 104.4, 106.6, 108.0 (4 d,
OCH2), 4.44 (mc, 0.3 H, cis-CHϭCH), 4.73 (mc, 3.7 H, trans-CHϭ 3Ј,3ЈЈ,5Ј,5ЈЈ-C), 120.6, 121.9 (2 s, 1Ј,1ЈЈ-C), 125.7, 126.1, 126.2 (3 d,
CH), 5.30 (s, 0.61 H, CH2Cl2), 6.5Ϫ6.7 (m with d at 6.57, J ϭ
3,5,6,8-C), 127.4, 127.4 (2 s, 4a,6a-C), 129.5, 129.6, 129.7 (3 d,
8.3 Hz, 4 H, 3Ј,3ЈЈ,5Ј,5ЈЈ-H), 7.1Ϫ7.3 (m with t at 7.22, J ϭ 8.3 Hz 4Ј,4ЈЈ-C, CHϭCH), 135.2, 135.3 (2 d, 4,7-C), 146.1, 146.3 (2 s,
and t at 7.24, J ϭ 8.3 Hz, 2 H, 4Ј,4ЈЈ-H), 7.5Ϫ7.7 (m with d at J ϭ 10a,10b-C), 155.0, 155.2 (2 s, 2,9-C), 158.0, 158.1, 158.1, 158.4 (4 s,
8.2 Hz, 2 H, 3,8-H), 7.8Ϫ7.9 (m with s at 7.83, 2 H, 5,6-H), 8.2Ϫ8.3 2Ј,2ЈЈ,6Ј,6ЈЈ-C) ppm. MS (EI, 70 eV): m/z (%) ϭ 532 (100) [Mϩ],
(m with d at 8.23, J ϭ 8.2 Hz, 2 H, 4,7-H) ppm. cis/trans-ratio:
450 (28) [Mϩ Ϫ C6H10], 424 (17) [C26H20N2O4]. HR-MS Ϫ
1:12. 13C NMR (125 MHz, CDCl3): δ ϭ 24.8, 25.0, 27.0, 30.5 (4 t, C34H32N2O4: found 532.23590, calcd. 532.23621 (δ ϭ 0.6 ppm);
CH2), 54.1 (t, CH2Cl2), 69.4, (t, OCH2), 104.6 (d, 3Ј,3ЈЈ,5Ј,5ЈЈ-C), C3313CH32N2O4: found 533.23890, calcd. 533.23956 (δ ϭ 1.2 ppm).
3124
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
Eur. J. Org. Chem. 2004, 3119Ϫ3127

Synthesis of Concave 1,10-Phenanthrolines
C34H32N2O4 (532.63): calcd. 76.67,
FULL PAPER
28.2 (t, OCH2CH2), 30.0 (t, CH2CHϭ), 56.0 (q, OCH3), 68.3 (t,
C
H
6.06,
N
5.26;
C34H32N2O4·0.6H2O (543.44): calcd. C 75.14, H 6.16, N 5.15; OCH2), 104.2, 105.3 (2 d, 3,5-C), 115.9 (t, ϭCH2), 133.0 (d, 4-C),
found C 75.37, H 6.35, N 4.82.
137.0 (d, CHϭ), 164.9, 165.5 (2 s, 2,6-C) ppm. Because of the
neighbouring 11B atom, the intensity of the 1-C signal was too
small to be recorded. MS (CI, isobutane): m/z (%) ϭ 237 (2)
[M ϩ Hϩ], 193 (100) [M ϩ Hϩ Ϫ HBO2]. MS (EI, 70 eV): m/z
(%) ϭ 192 (27) [Mϩ Ϫ HBO2], 124 (100) [Mϩ Ϫ C5H9BO2].
C12H17BO4 (236.07): calcd. C 61.05, H 7.26; C12H17BO4·0.4H2O
(236.08): calcd. 59.24, H 7.37; found C 59.11, H 7.38.
2-Bromo-3-methoxyphenol (6): 2-Bromo-1,3-dihydroxybenzene[25]
(5, 10.0 g, 52.9 mmol) was added to a solution of potassium hy-
droxide (3.70 g, 66.1 mmol) in water (35 mL). Then dimethyl sul-
fate (5.00 mL, 52.7 mmol) was added slowly so that the tempera-
ture remained between 10 and 20 °C. After 30 min stirring at 100
°C, 2  sodium hydroxide was added until the pH of the solution
was basic. This mixture was extracted three times with dichloro-
methane (50 mL). The aqueous layer was then acidified with 2 
hydrochloric acid and the layers separated. The aqueous layer was
extracted three times with diethyl ether (50 mL). The combined or-
ganic fractions were dried with magnesium sulfate. The solvents
were evaporated in vacuo and the residue was purified by chroma-
tography (silica gel, cyclohexane/ethyl acetate, 3:1), giving 5.48 g
(51%) of 6. M.p. 76 °C, ref.[27] 78.5Ϫ79 °C. GC (Optima 1/25 m,
temp. program: 5 min at 100 °C, 10 °C/min until 250 °C, 20 min):
tRet ϭ 7.9 min, purity 89%. IR (KBr): ν˜ ϭ 3403 (OϪH), 3010
(arom. CϪH), 2972, 2940 (aliph. CϪH), 1593, 1467 (arom. CϭC),
1198 (OϪH), 1080 (CϪOϪC), 1032 (arom. CϪBr) cmϪ1. 1H NMR
(200 MHz, CDCl3): δ ϭ 3.89 (s, 3 H, OCH3), 5.66 (s, 1 H, OH),
6.48 (dd, J ϭ 1.3, J ϭ 8.3 Hz, 1 H, 4-H), 6.58Ϫ6.70 (m, 1 H, 6-H),
7.06Ϫ7.26 (m, 1 H, 5-H) ppm. MS (EI, 70 eV): m/z (%) ϭ 204, 202
(95, 100) [Mϩ], 189, 187 (10, 12) [Mϩ Ϫ CH2].
2-Bromo-3-(methoxymethoxy)phenol (9): A solution of 2-bromo-
1,3-dihydroxybenzene (5, 1.00 g, 5.29 mmol) in dry N,N-dimeth-
ylformamide (5 mL) was slowly added to a suspension of sodium
hydride (212 mg, 53 mmol, 60% in mineral oil, washed three times
with pentane) in dry tetrahydrofuran (10 mL) at 0 °C. After stirring
for 1 h at room temp., methoxymethyl chloride (400 µL,
5.27 mmol) was added at 0 °C. After additional stirring at room
temp. for 2 h, aqueous 2  ammonium chloride (10 mL) was added,
the layers were separated, and the aqueous layer was extracted
three times with diethyl ether (30 mL). After drying of the com-
bined organic layer with magnesium sulfate, the solvent was evapo-
rated in vacuo and the crude product was purified by chromatogra-
phy (silica gel, cyclohexane/ethyl acetate, 10:1) yielding 405 mg
(33%) of 9, m.p. 55Ϫ56 °C. IR (film): ν˜ ϭ 3355 (OϪH), 2969, 2925
(aliph. CϪH), 1594, 1580, 1477 (arom. CϭC), 1148, 1087 (CϪO),
1
1040 (arom. C-Br) cmϪ1. H NMR (300 MHz, CDCl3): δ ϭ 3.51
(s, 3 H, OCH3), 5.24 (s, 2 H, OCH2O), 5.70 (s, 1 H, OH), 6.70Ϫ6.73
(m, 2 H, 4,6-H), 7.11Ϫ7.17 (m, 1 H, 5-H) ppm. 13C NMR
(75 MHz, CDCl3): δ ϭ 56.4 (q, OCH3), 95.0 (t, OCH2O), 101.3 (s,
2-C), 107.4, 109.4 (2 d, 4,6-C), 128.7 (d, 5-C), 153.5, 154.3 (2 s, 1,3-
C) ppm. MS (EI, 70 eV): m/z (%) ϭ 234, 232 (98, 100) [Mϩ], 204,
202 (56, 58) [Mϩ Ϫ OCH2], 189, 187 (9, 11) [Mϩ Ϫ OC2H5], 174,
172 (16, 22) [Mϩ Ϫ O2C2H4]. HR-MS Ϫ C8H979BrO3: found
231.97350, calcd. 231.97351 (δ ϭ 0.0 ppm); C8H981BrO3: found
233.97130, calcd. 233.97147 (δ ϭ 0.7 ppm). C8H9BrO3 (233.06):
calcd. C 41.23, H 3.89; found C 41.74, H 4.18.
2-Bromo-1-methoxy-3-(pent-4-enyloxy)benzene (7): Batch size: 2-
bromo-3-methoxyphenol (893 mg, 4.40 mmol, 6) in dry N,N-di-
methylformamide (20 mL), using potassium carbonate (1.82 g,
8.80 mmol), potassium iodide (500 mg, 3.01 mmol) and 5-bromo-
1-pentene (650 µL, 5.50 mmol). Purification: chromatography on
silica gel eluting with cyclohexane/ethyl acetate (15:1) . Yield 1.31 g
(94%). GC (SE30/25 m, temp. program (5 min at 100 °C, 10 °C/
min until 250 °C, 20 min at 250 °C): tRet ϭ 14.6 min, purity: 96%.
IR (film): ν˜ ϭ 3076 (arom. CϪH), 2940, 2839 (aliph. CϪH), 1640
(aliph. CϭC), 1592, 1469 (arom. CϭC), 1102 (CϪOϪC), 1036
2-Bromo-1-(hex-5-enyloxy)-3-(methoxymethoxy)benzene (10): Batch
size: 2-bromo-3-(methoxymethoxy)phenol (9, 254 mg, 1.09 mmol)
in dry N,N-dimethylformamide (10 mL) using potassium carbonate
(452 mg, 3.27 mmol), potassium iodide (166 mg, 1.00 mmol) and
6-bromo-1-hexene (182 µL, 1.36 mmol). Purification: chromatogra-
phy on silica gel eluting with cyclohexane/ethyl acetate (10:1). Yield
332 mg (97%). GC (Optima 1/25 m, temp. program (5 min at 100
°C, 10 °C/min until 250 °C, 20 min at 250 °C): tRet ϭ 17.4 min,
purity: 96%. IR (film): ν˜ ϭ 2934 (aliph. CϪH), 1640 (aliph. Cϭ
C), 1594, 1463 (arom. CϭC), 1096, 1069 (CϪOϪC), 1037 (arom.
1
(arom. CϪBr) cmϪ1. H NMR (300 MHz, CDCl3): δ ϭ 1.94 (mc,
2 H, OCH2CH2), 2.30 (mc, 2 H, CH2CHϭ), 3.90 (s, 3 H, OCH3),
4.04 (t, J ϭ 6.3 Hz, 2 H, OCH2), 5.00, 5.07 (tdd, Jt ϭ 1.2, Jd ϭ 2.0,
Jd ϭ 10.2 Hz, ϭCHHcis, tdd, Jt ϭ 1.5, Jd ϭ 2.0, Jd ϭ 17.2 Hz, ϭ
CHHtrans, 2 H), 5.87 (tdd, Jt ϭ 6.7, Jd ϭ 10.2, Jd ϭ 17.2 Hz, 1 H,
CHϭ), 6.56 (mc, 2 H, 4,6-H), 7.20 (t, J ϭ 8.3 Hz, 1 H, 5-H) ppm.
13C NMR (75 MHz, CDCl3): δ ϭ 28.9 (t, OCH2CH2), 30.4 (t,
CH2CHϭ), 56.4 (q, OCH3), 68.4 (t, OCH2), 101.5 (s, 2-C), 104.5,
105.9 (2 d, 4,6-C), 115.3 (t, ϭCH2), 128.1 (d, 5-C), 137.7 (d,
CHϭ), 156.6, 157.2 (2 s, 1,3-C) ppm. MS (EI, 70 eV): m/z (%) ϭ
272, 270 (3, 4) [Mϩ], 204, 202 (85, 88) [Mϩ Ϫ C5H8], 191 (100)
[Mϩ Ϫ Br]. C12H18BrO2 (271.15): calcd. C 53.15, H 5.58; found C
53.25, H 5.59.
CϪBr) cmϪ1 1H NMR (300 MHz, CDCl3): δ ϭ 1.63 (mc, 2 H,
.
OCH2CH2CH2), 1.85 (mc, 2 H, OCH2CH2), 2.16 (mc, 2 H,
CH2CHϭ), 3.52 (s, 3 H, OCH3), 4.03 (t, J ϭ 6.4 Hz, 2 H, OCH2),
4.95Ϫ5.08 (m, 2 H, ϭCH2), 5.25 (s, 2 H, OCH2O), 5.84 (tdd, Jt ϭ
6.7, Jd ϭ 10.2, Jd ϭ 17.1 Hz, 1 H, CHϭ), 6.58 (dd, J ϭ 1.2, J ϭ
8.3 Hz, 1 H, 6-H), 6.78 (dd, J ϭ 1.2, J ϭ 8.3 Hz, 1 H, 4-H), 7.17
(t, J ϭ 8.3 Hz, 1 H, 5-H) ppm. 13C NMR (75 MHz, CDCl3): δ ϭ
2-Methoxy-6-(pent-4-enyloxy)benzeneboronic acid (8): Batch size: 2-
bromo-1-methoxy-3-(pent-4-enyloxy)benzene (7, 1.00 g, 3.67
mmol) in tetrahydrofuran (15 mL) using n-butyllithium (2.5  in n-
hexane, 1.60 mL, 4.00 mmol) and trimethylborate (1.40 mL, 25.3 (t, OCH2CH2CH2), 28.5 (t, OCH2CH2), 33.4 (t, CH2CHϭ),
12.6 mmol). Purification: chromatography on silica gel eluting with
cyclohexane/ethyl acetate (6:1). The compound was very hygro-
scopic. Yield 57%. M.p. 36Ϫ37 °C. IR (KBr): ν˜ ϭ 3507 (OϪH),
3075 (arom. CϪH), 2999, 2941, 2837 (aliph. CϪH), 1640 (aliph.
56.4 (q, OCH3), 69.1 (t, OCH2), 95.1 (t, OCH2O), 103.0 (s, 2-C),
106.7 (d, 6-C), 108.3 (d, 4-H), 114.7 (t, ϭCH2), 128.1 (d, 5-H),
138.6 (d, CHϭ), 155.0, 156.7 (2 s, 1,3-C) ppm. MS (EI, 70 eV):
m/z (%) ϭ 316, 314 (10, 9) [Mϩ], 235 (100) [Mϩ Ϫ Br]. HR-MS Ϫ
CϭC), 1598 (arom. CϭC), 1102 (CϪOϪC) cmϪ1 1H NMR C14H1979BrO3: found 314.05160, calcd. 314.05176 (δ ϭ 0.5 ppm);
.
(300 MHz, CDCl3): δ ϭ 1.96 (mc, 2 H, OCH2CH2), 2.25 (mc, 2 H, C1313CH1979BrO3: found 315.05500, calcd. 315.05511 (δ
ϭ
CH2CHϭ), 3.91 (s, 3 H, OCH3), 4.09 (t, J ϭ 6.5 Hz, 2 H, OCH2), 0.4 ppm); C14H1981BrO3: found 316.04960, calcd. 316.04971 (δ ϭ
4.99Ϫ5.12 (mc, 2 H, ϭCH2), 5.82 (tdd, Jt ϭ 6.7, Jd ϭ 10.2, Jd ϭ
17.1 Hz, 1 H, CHϭ), 6.62 (mc, 2 H, 3,5-H), 7.29 (s, 2 H, OH), 7.37
0.4 ppm); C1313CH1981BrO3: found 317.05300, calcd. 317.05307
(δ ϭ 0.2 ppm). C14H19BrO3 (315.20): calcd. C 53.35, H 6.08; found
(t, J ϭ 8.4 Hz, 1 H, 4-H) ppm. 13C NMR (75 MHz, CDCl3): δ ϭ C 53.92, H 5.90.
Eur. J. Org. Chem. 2004, 3119Ϫ3127
www.eurjoc.org
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
3125

U. Lüning, F. Fahrenkrug
FULL PAPER
2-Bromo-3-(hex-5-enyloxy)phenol (11): 2-Bromo-1-(hex-5-enyloxy)-
IR (KBr): ν˜ ϭ 3504 (OϪH), 3073 (arom. CϪH), 2944, 2879 (aliph.
3-(methoxymethoxy)benzene (10, 280 mg, 892 µmol) was dissolved CϪH), 1643 (aliph. CϭC), 1596, 1575 (arom. CϭC), 1101
in tetrahydrofuran (10 mL). After addition of trifluoroacetic acid
(CϪOϪC) cmϪ1. 1H NMR (300 MHz, CDCl3): δ ϭ 1.52 [mc, 2 H,
(100 µL, 1.26 mmol) and water (1.5 mL), the mixture was heated O(CH2)2CH2CH2CHϭ], 1.79 [mc, 2 H, OCH2CH2(CH2)2CHϭ],
at reflux for 16 h. Following completion of the reaction, the solvent
and trifluoroacetic acid were evaporated in vacuo and the crude
product was purified by chromatography (silica gel, cyclohexane/
ethyl acetate, 6:1). Yield 215 mg (89%). IR (film): ν˜ ϭ 3498 (OϪH),
2.06 [mc, 2 H, O(CH2)3CH2CHϭ], 2.53 (tq, Jt ϭ 1.4, Jq ഠ
6 Hz, 2 H, OCH2CH2CHϭ), 3.99 [t, 6.6 Hz, 2 H,
OCH2(CH2)3CHϭ], 4.06 (t, J ϭ 6.3 Hz, 2 H, OCH2CH2CHϭ),
4.88Ϫ4.99 [m, 2 H, O(CH2)4CHϭCH2], 5.09Ϫ5.21 [m, 2 H,
J
ϭ
3074 (arom. CϪH), 2938 (aliph. CϪH), 1639 (aliph. CϭC), 1594, O(CH2)2CHϭCH2], 5.66Ϫ5.86 (m, 2 H, CHϭ), 6.52, 6.53 (2 d, J ϭ
1461 (arom. CϭC), 1200 (arom. CϪOH), 1075 (CϪOϪC), 1031 8.4, J ϭ 8.4 Hz, 2 H, 3,5-H), 7.21 (s, 2 H, OH), 7.27 (t, J ϭ 8.4 Hz,
1
(arom. CϪBr) cmϪ1. H NMR (300 MHz, CDCl3): δ ϭ 1.61 (mc, 1 H, 4-H) ppm. 13C NMR (75 MHz, CDCl3): δ ϭ 24.2 [t,
2 H, OCH2CH2CH2), 1.84 (mc, 2 H, OCH2CH2), 2.14 (mc, 2 H, O(CH2)2CH2CH2CHϭ], 27.5 [t, OCH2CH2(CH2)2CHϭ], 32.3,
CH2CHϭ), 4.01 (t, J ϭ 6.3 Hz, 2 H, OCH2), 4.95Ϫ5.08 (m, 2 H, ϭ 32.7 (2 t, CH2CHϭ), 66.7, 67.9 (2 t, OCH2), 103.9, 104.2 (2 d, 3,5-
CH2), 5.65 (s, 1 H, OH), 5.84 (tdd, Jt ϭ 6.6, Jd ϭ 10.2, Jd ϭ
17.1 Hz, 1 H, CHϭ), 6.58 (dd, J ϭ 1.3, J ϭ 8.3 Hz, 1 H, 4-H), 137.0 (2 d, CHϭ), 163.9, 163.9 (2 s, 2,6-C) ppm. MS (EI, 70 eV):
6.66 (dd, J ϭ 1.3, J ϭ 8.3 Hz, 1 H, 6-H), 7.13 (t, Jt ϭ 8.3 Hz, 1 H, m/z (%) ϭ 290 (28) [Mϩ], 246 (45) [Mϩ Ϫ HBO2], 207 (6) [Mϩ
5-H) ppm. 13C NMR (75 MHz, CDCl3): 25.2 (t, C6H11], 154 (73) [Mϩ Ϫ C10H16], 83 (100) [C6H11], 69 (99) [C5H9].
C), 105.6 (s, 1-C), 114.1, 117.3 (2 t, ϭCH2), 131.9 (d, 4-H), 132.7,
Ϫ
δ
ϭ
OCH2CH2CH2), 28.5 (t, OCH2CH2), 33.3 (t, CH2CHϭ), 69.0 (t, C16H23BO4 (290.17): calcd. C 66.23, H 7.99; found C 66.16, H 8.18.
OCH2), 100.5 (s, 2-C), 104.6 (d, 4-C), 108.3 (d, 6-H), 114.8 (t, ϭ
2-[2,6-Bis(hex-5-enyloxy)phenyl]-9-chloro-1,10-phenanthroline (16):
2,9-Dichloro-1,10-phenanthroline (14, 564 mg, 2.30 mmol) was dis-
solved in dimethoxyethane (50 mL), and 2,6-bis(hex-5-enyloxy)-
benzeneboronic acid 15[22] (793 mg, 2.49 mmol), tetrakis(triphenyl-
phosphane)palladium(0) (266 mg, 230 µmol) and 2  aqueous so-
dium carbonate (2.3 mL) were added. The mixture was heated at
reflux for 16 h before water (20 mL) and dichloromethane (25 mL)
were added. The layers were separated and the aqueous layer was
extracted three times with dichloromethane (30 mL). The combined
organic layer was washed with brine (20 mL) and dried with mag-
CH2), 128.6 (d, 5-H), 138.5 (d, CHϭ), 153.5, 156.0 (2 s, 1,3-C)
ppm. MS (EI, 70 eV): m/z (%) ϭ 272, 270 (9, 10) [Mϩ], 190, 188
(93, 100) [Mϩ Ϫ C6H10]. C12H15BrO2 (271.15): calcd. C 53.16, H
5.58; found C 52.87, H 5.73.
2-Bromo-1-(but-3-enyloxy)-3-(hex-5-enyloxy)benzene
(12):
2-
Bromo-3-(hex-5-enyloxy)phenol (11, 1.61 g, 5.95 mmol), 3-buten-1-
ol (770 µL, 9.00 mmol) and triphenylphosphane (2.03 g,
7.74 mmol) were dissolved in tetrahydrofuran (20 mL). At 0 °C,
diethyl azodicarboxylate (1.20 mL, 7.72 mmol) dissolved in tetra-
hydrofuran (5 mL) was added and the mixture was stirred for 2 h nesium sulfate. After evaporation to dryness, the crude product was
at room temp. After addition of water (20 mL), the layers were
separated and the aqueous layer was extracted three times with
dissolved in dichloromethane, filtered through basic alumina and
purified by chromatography (dichloromethane with 0.5% of meth-
diethyl ether (20 mL). The combined organic layer was washed anol, silica gel) and recrystallized from dichloromethane/hexane.
three times with 2  sodium hydroxide (20 mL) and once with brine
(20 mL). After drying with magnesium sulfate, the solvent was eva-
porated in vacuo and the residue was purified by chromatography
(cyclohexane/ethyl acetate, 9:1, silica gel). Yield 1.23 mg (64%). IR
Yield 878 mg (78%). M. p. 98Ϫ100 °C. IR (KBr): ν˜ ϭ 3071 (arom.
CϪH), 2934, 2869 (aliph. CϪH), 1640 (aliph. CϭC), 1582, 1477,
1456 (arom. CϭC), 1096 (CϪOϪC) cmϪ1 1H NMR (500 MHz,
.
CDCl3): δ ϭ 1.34 (mc, 4 H, OCH2CH2CH2), 1.57 (mc, 4 H,
(film): ν˜ ϭ 3076 (arom. CϪH), 2975, 2935 (aliph. CϪH), 1640 OCH2CH2), 1.84 (mc, 4 H, CH2CHϭ), 4.00 (t, J ϭ 6.3 Hz, 4 H,
(aliph. CϭC), 1592, 1459 (arom. CϭC), 1097 (CϪOϪC),
OCH2), 4.7Ϫ4.8 (m, 4 H, ϭCH2), 5.51 (tdd, Jt ϭ 6.7, Jd ϭ 10.3,
Jd ϭ 17.1 Hz, 2 H, CHϭ), 6.67 (d, J ϭ 8.4 Hz, 2 H, 3Ј,5Ј-H), 7.30
1036 (arom. CϪBr) cmϪ1 1H NMR (300 MHz, CDCl3): δ ϭ
.
1.62 (mc, 2 H, O(CH2)2CH2CH2CHϭ), 1.85 [mc, 2 H, (t, J ϭ 8.4 Hz, 1 H, 4Ј-H), 7.55 (d, J ϭ 8.4 Hz, 1 H, 8-H), 7.73 (d,
OCH2CH2(CH2)2CHϭ], 2.14 [mc, 2 H, O(CH2)3CH2CHϭ], 2.59 J ϭ 8.3 Hz, 1 H, 3-H), 7.74 (d, J ϭ 8.8 Hz, 1 H, 5-H or 6-H), 7.82
(tq, Jt ϭ 1.3, Jq ഠ 7 Hz, 2 H, OCH2CH2CHϭ), 4.00 [t, J ഠ 7 Hz, (d, J ϭ 8.8 Hz, 1 H, 6-H or 5-H), 8.16 (d, J ϭ 8.4 Hz, 1 H, 7-H),
2 H, OCH2(CH2)3CHϭ], 4.06 (t, J ഠ 7 Hz, 2 H, OCH2CH2CHϭ),
8.20 (d, J ϭ 8.3 Hz, 1 H, 4-H) ppm. 13C NMR (125 MHz, CDCl3):
4.95Ϫ5.07 [m, 2 H, O(CH2)4CHϭCH2], 5.09Ϫ5.22 [m, 2 H, δ ϭ 25.1 (t, OCH2CH2CH2), 28.5 (t, OCH2CH2), 33.2 (t, CH2-
O(CH2)2CHϭCH2], 5.83 [tdd, Jt ϭ 6.7, Jd ϭ 10.2, Jd ϭ 17.1 Hz, CHϭ), 69.0 (t, OCH2), 106.1 (d, 3Ј,5Ј-C), 114.1 (t, ϭCH2), 120.7
1 H, OCH2(CH2)3CHϭ], 5.95 (tdd, Jt ϭ 6.8, Jd ϭ 10.3, Jd ϭ
(s, 1Ј-C), 123.8, 125.0, 127.0, 127.1 (4 d, 3,5,6,8-C), 127.3, 127.6
17.1 Hz, 1 H, OCH2CH2CHϭ), 6.53 (d, J ϭ 8.3 Hz, 2 H, 4,6-H), (2 s, 4a,6a-C), 129.9 (d, 4Ј-C), 134.7, 138.5 (2 d, 4,7-C), 138.6 (d,
7.16 (t, J ϭ 8.3 Hz, 2 H, 5-H) ppm. 13C NMR (75 MHz, CHϭ), 144.7, 146.3 (2 s, 10a,10b-C), 150.9, 155.7 (2 s, 2,9-C), 158.1
CDCl3):
δ
ϭ
25.2 [t, O(CH2)2CH2CH2CHϭ], 28.5 [t,
(s, 2Ј,6Ј-C) ppm. MS (EI, 70 eV): m/z (%) ϭ 488, 486 (31, 76) [Mϩ],
OCH2CH2(CH2)2CHϭ], 33.5, 33.6 (2 t, CH2CHϭ), 68.6, 69.1 (2 t, 419, 417 (37, 100) [Mϩ Ϫ C5H9], 405, 403 (42, 95) [Mϩ Ϫ C6H11].
OCH2), 102.2 (s, 2-C), 105.8, 105.8 (2 d, 4,6-C), 114.7, 117.2 (2 t, ϭ
CH2), 128.0 (d, 5-H), 134.2, 138.6 (2 d, CHϭ), 156.6, 156.7 (2 s,
1,3-C) ppm. MS (CI, isobutane): m/z (%) ϭ 327, 325 (61, 61)
HR-MS Ϫ C30H3135ClN2O2: found 486.20680; calcd. 486.20740
(δ
1.2 ppm); C30H3137ClN2O2: found 488.20340, calcd.
488.20447 (δ ϭ 0.3 ppm). C30H31ClN2O2 (487.04): calcd. C 73.98,
ϭ
[M ϩ Hϩ]. MS (EI, 70 eV): m/z (%) ϭ 326, 324 (3, 4) [Mϩ], 245 H 6.42, N 5.75; found C 73.69, H 6.57, N 5.61.
(75) [Mϩ Ϫ Br], 190, 188 (100, 99) [Mϩ Ϫ C10H16]. C16H21BrO2
(325.25): calcd. C 59.09, H 6.51; found C 58.93, H 7.04.
[1]
See textbooks of biochemistry, e.g.: D. Voet, J. G. Voet, C. W.
2-(But-3-enyloxy)-6-(hex-5-enyloxy)benzeneboronic Acid (13): Batch
size: 2-bromo-1-(but-3-enyloxy)-3-(hex-5-enyloxy)benzene (12,
1.09 g, 3.34 mmol) in tetrahydrofuran (15 mL) using n-butyllithium
Pratt, Lehrbuch der Biochemie, Wiley-VCH, Weinheim, 2002.
J. W. Steed, J. L. Atwood, Supramolecular Chemistry, John
Wiley & Sons, Chichester, New York, Weinheim, Brisbane, Sin-
gapore, Toronto, 2000.
J.-M. Lehn, Supramolecular Chemistry, VCH, Weinheim, New
York, Basel, Cambridge, Tokyo, 1995.
[2]
[3]
(2.5
 in hexane, 1.50 mL, 3.75 mmol) and trimethylborate
(1.25 mL, 11.2 mmol). Purification: chromatography on silica gel
eluting with cyclohexane/ethyl acetate (6:1). Yield 78%. M.p. 41 °C.
3126
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
Eur. J. Org. Chem. 2004, 3119Ϫ3127

Synthesis of Concave 1,10-Phenanthrolines
FULL PAPER
ladium-Catalyzed Organic Reactions, Academic Press, San Di-
ego, London, New York, Boston, Sydney, Tokyo, Toronto,
1997.
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S. Toyota, C. R. Woods, M. Benagalia, J. S. Siegel, Tetrahedron
Lett. 1998, 39, 2697Ϫ2700.
J. Lewis, T. D. O’Donoghue, J. Chem. Soc., Dalton Trans.
1980, 736Ϫ742.
E. Kiehlmann, R. W. Lauener, Can. J. Chem. 1989, 67,
335Ϫ344.
Comment: all (concave) 1,10-phenanthrolines tend to absorb
water or, in some cases, also solvent molecules. Solvent content
was estimated from NMR integrals, and the water content was
calculated from the elemental analyses.
[4]
Comprehensive Supramolecular Chemistry (Ed.: J. L. Atwood),
Pergamon Press, Oxford, 1996, ff.
[5]
F. Vögtle, Supramolekulare Chemie, Teubner, Stuttgart, 1989.
[6]
[18]
[19]
U. Lüning, M. Müller, M. Gelbert, K. Peters, H. G. von
Schnering, M. Keller, Chem. Ber. 1994, 127, 2297Ϫ2306.
[7]
M. Hagen, U. Lüning, Chem. Ber./Recueil 1997, 130, 231Ϫ234.
[8]
[20]
M. Gelbert, U. Lüning, Supramolecular Chem. 2001, 12,
435Ϫ444.
B. Meynhardt, U. Lüning, C. Wolff, C. Näther, Eur. J. Org.
[9]
[21]
[22]
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