Concave 1,10-phenanthrolines as ligands for cyclopropanations - Towards a deeper understanding of the stereoselectivity

Article abstract of DOI:10.1002/ejoc.200801261

Four new mono- and bimacrocyclic 1,10-phenanthrolines - 3b and 4a-c - containing aryl bridgeheads have been synthe- sised. The etherification of the aryl bridgeheads was accomplished by Williamson or Mitsunobu reactions. A key step in the synthesis of the macrocyclic phenanthrolines 3 and 4 is the Suzuki coupling of 2,9-diiodo-1,10-phenan- throline (12) with the appropriately substituted boronic acids 17 and 20. Ring-closing metathesis and hydrogenation completed the synthesis. The resulting macrocyclic 1,10-phenan- throlines 3b and 4a-c were tested as ligands in a copper(I)- catalysed stereoselective cyclopropanation.

Full text of DOI:10.1002/ejoc.200801261

FULL PAPER
DOI: 10.1002/ejoc.200801261
Concave 1,10-Phenanthrolines as Ligands for Cyclopropanations –
Towards a Deeper Understanding of the Stereoselectivity[‡]
Friederike Eggers[a] and Ulrich Lüning*[a]
Keywords: Cyclopropanation / Heterocycles / Macrocycles / 1,10-Phenanthroline / Supramolecular chemistry
Four new mono- and bimacrocyclic 1,10-phenanthrolines –
17 and 20. Ring-closing metathesis and hydrogenation com-
3b and 4a–c – containing aryl bridgeheads have been synthe-
pleted the synthesis. The resulting macrocyclic 1,10-phenan-
sised. The etherification of the aryl bridgeheads was ac- throlines 3b and 4a–c were tested as ligands in a copper(I)-
complished by Williamson or Mitsunobu reactions. A key
catalysed stereoselective cyclopropanation.
step in the synthesis of the macrocyclic phenanthrolines 3
and 4 is the Suzuki coupling of 2,9-diiodo-1,10-phenan- (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
throline (12) with the appropriately substituted boronic acids
Germany, 2009)
Introduction
One of the most important goals in organic chemistry is
the enhancement of selectivity in order to optimise yield,
solvent requirements, catalyst loading etc. The best exam-
ples of highly selective catalysts are to be found among en-
zymes. Their fascinating selectivities are due to the geome-
tries of their active sites,[1] which are often described as
cleft-, cave- or hole-like. All these geometric features can be
summarised in the word “concave”.[2–5]
In mimicry of the geometries of enzymes, several classes
of concave reagents[6] with their reactive sites shielded in
varying geometries have been developed, with the goal of
enhancing selectivities both in catalyses and also in stoi-
chiometric reactions. A well investigated and successful
class of ligands for catalytically active metals is the group of
concave bimacrocyclic 1,10-phenanthrolines (see Figure 1),
some of which show remarkable selectivities.[7–11] 1,10-
Phenanthroline itself possesses two nitrogen atoms and is
therefore a good chelating ligand for transition metal ions
such as copper(I).
Figure 1. Classes of macrocyclic 1,10-phenanthrolines.
Several sub-classes of bimacrocyclic concave 1,10-phen-
anthrolines have been synthesised; they include bimacro-
cyclic bislactams,[12] bimacrocyclic cyclophanes 1 with aryl
bridgeheads,[7,13] and bimacrocyclic bridged calixarenes
2.[14,15] The last two classes have been employed as ligands
in copper(I)-catalysed cyclopropanations of alkenes such as
styrene or indene with diazoacetates;[8,11,16,17,18] some re-
markable selectivities have been achieved. Whereas the cy-
clophane-derived ligands 1 exhibited strong anti selectivities
(up to 140:1), the calixarene derivatives 2 were able to pro-
duce the syn products predominantly (best value: 86:14).
In a combined computational and experimental study,[16]
two models that explain these anti and syn selectivities were
developed. The striking differences between the two classes
of catalysts were their different rigidities and their different
symmetries. Figure 2 shows the different orientations of the
1,10-phenanthroline planes with respect to the macrocycles
that they bridge. In the left-hand structure in Figure 2, the
symmetry of the cyclophane 1b with aryl bridgeheads be-
comes obvious. If a copper(I) ion were bound to the nitro-
[‡] Concave Reagents, 58. Part 57: O Winkelmann, C. Näther,
U. Lüning, Org. Biomol. Chem. 2009, 553–556.
[a] Otto-Diels-Institut für Organische Chemie,
Christian-Albrechts-Universität zu Kiel,
Ohlshausenstr. 40, 24098 Kiel
Fax: +49-431-880-1558
E-mail: luening@oc.uni-kiel.de
2328
© 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 2009, 2328–2341

Concave 1,10-Phenanthrolines as Ligands for Cyclopropanations
gen atoms of the 1,10-phenanthroline it would be located rather resemble those of the calixarene derivatives. Figure 2
between the bridgeheads in the same way as the cyclopro- shows that the ortho,para-bridged cyclophane 3 possesses
panation intermediate, the copper(I) carbene complex, such a different geometry in relation to the ortho,ortho-
would have to (for details on the cyclopropanation reaction bridged cyclophane 1 and the calixarene derivative 2. The
see Figure 9, below). If a diazoacetate is used for the cyclo- goal of this work was therefore to synthesise members of
propanation, the ester group of the carbene has to be ac- this new class of unsymmetrical bimacrocyclic 1,10-phenan-
commodated in the complex. In the concave environment throline cyclophanes.
of the complex, the ester group can only stretch out of bi-
macrocycle 1b to the “south” (in the orientation shown in
Figure 2). An incoming alkene would have to avoid steric
compression with this residue, and the resulting maximi-
Results and Discussion
sation of distance between alkene and ester group explains
the anti selectivity.
Synthesis of the Starting Materials
The building blocks for the new macrocyclic 1,10-phen-
anthrolines 3 and 4 were 2,9-diiodo-1,10-phenanthroline
(12, Figure 4, below) and the variously substituted phen-
ylboronic acids 17 and 20 (Figure 5, below). 2,9-Diiodo-
1,10-phenanthroline (12) was synthesised by the well known
procedure described by Lewis et al.[20] and Yamada et al.[21]
From 1,10-phenanthroline (5), chloro atoms were first in-
troduced at the 2- and 9-positions to yield phenanthroline
10, and then a chloro–iodo exchange was accomplished (see
Figures 3 and 4).
Figure 2. Geometry-optimised models of three classes of 1,10-
phenanthroline-containing bimacrocycles. All bimacrocycles are
oriented in the same way with respect to the 1,10-phenanthroline
bridge. Whereas the bimacrocycle with ortho,ortho-disubstituted
bridgeheads (1b, left) is symmetric, the other two classes – a 1,10-
phenanthroline-bridged calix[6]arene (2a, middle) and a bimacro-
cycle with ortho,para-disubstituted bridgeheads (3a, right) – possess
openings next to their 1,10-phenanthroline components (to the
“west”) but are shielded in the “south”. For implications see text.
The 1,10-phenanthroline-bridged calix[6]arene 2a is
shown in the middle of Figure 2. Its geometric differences
from the bimacrocyclic cyclophane 1b on the left are obvi-
ous. Because of the O–CH2 link between the 1,10-phen-
anthroline and the calixarene aryl rings, the 1,10-phen-
anthroline bridge can tilt to the side, thus generating an
opening next to the 1,10-phenanthroline. If a copper(I) ion
were bound here and were to react with a diazoacetate, the
ester group would have to be accommodated in the area
between the 1,10-phenanthroline and the calixarene rim.
An incoming alkene would again try to avoid the ester
group, but the geometry is not symmetric. The ester group
would point towards the incoming alkene, but the alterna-
tive approach would be strongly shielded by the large ca-
lix[6]arene moiety. If the ester group were to carry only a
small residue, the repulsion by the calixarene would domi-
nate and this would result in the formation of a syn prod- Figure 3. 2,9-Dichloro-1,10-phenanthroline (10) can be synthesised
uct.[16]
in two different ways starting from 1,10-phenanthroline (5).
Unfortunately, calixarenes cannot be altered too much.
The ring size, for instance, can only be changed in relatively
large steps by addition or removal of one arylmethylene
block. Bridging experiments have been carried out for ca-
lix[5]- and calix[8]arenes,[19] but the resulting products were
not comparable with the nice bimacrocyclic calix[6]arenes 2
used so effectively in the catalyses.
We therefore thought about alteration of the cyclophane
bimacrocycles 1 in such a way that their geometries would yield 58%; b) NaI, HI, 16 h, 100 °C, yield 48%.
Figure 4. Transformation of 2,9-dichloro-1,10-phenanthroline (10)
into 2,9-diiodo-1,10-phenanthroline (12). a) NaI, HI, 4 d, 80 °C,
Eur. J. Org. Chem. 2009, 2328–2341
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F. Eggers, U. Lüning
FULL PAPER
The different phenylboronic acids 17 and 20 were synthe- Table 2. Workup conditions and yields for the syntheses of phen-
ylboronic acids 17 and 20.
sised from resorcinol (13) or from 4-bromophenol (18). Res-
orcinol (13) was first halogenated with iodine monochloride
to yield the desired product, 4-iodoresorcinol (14b), in
about 40% yield. 4-Bromoresorcinol (14a), which is com-
mercially available, can also be used in the following step. 16c
The phenol groups of the halogenated aromatic compounds
14 were alkylated by the Williamson or Mitsunobu strate-
gies. In the case of iodoarenes, Williamson alkylation is re-
commended because the Mitsunobu coupling of an alcohol
with an iodophenol gave only a very low yield.
Arene Workup
Boronic acid
% Yield
16a
16b
–
–
–
17a
17b
17b
crude product
crude product
crude product
84
90
78
[a]
19a
recrystallisation
recrystallisation
recrystallisation
20a
[a]
19b
20b
[a]
19c
20c
[a] The boronic acids 19a–c crystallise as mixtures of monomers
and trimers of the boronic acids, as was shown by their mass and
NMR spectra.
Figure 5 summarises the syntheses of the phenylboronic
acids 17 and 20, whereas Table 1 lists the reaction condi-
tions and the yields corresponding to the different alken-
oxyarenes 16 and 19 and Table 2 gives the workup condi-
tions and yields for the syntheses of the different boronic
acids 17 and 20.
Suzuki Coupling and Ring-Closure
After the starting materials had been synthesised, Suzuki
reactions were used to couple the boronic acids 17 and 20
to the 1,10-phenanthroline unit (Figure 6). 2,9-Diiodo-1,10-
phenanthroline (12) was used in most couplings, because of
its higher reactivity relative to 2,9-dichloro-1,10-phen-
anthroline (10). In one reaction with dichloride 10 and bo-
ronic acid 17b, monoarylated 1,10-phenanthroline 23 could
be isolated (Figure 7). In a subsequent reaction, this inter-
mediate could also be transformed into the desired 2,9-di-
aryl-1,10-phenanthroline 21b by a second Suzuki coupling
with boronic acid 17b. The Suzuki couplings[22] were carried
out in mixtures of 1,2-dimethoxyethane and water (4:1).
Tetrakis(triphenylphosphane)palladium(0) was chosen as
catalyst, and barium hydroxide was used as base. Because
of the instabilities of the disubstituted phenylboronic acids
17 during column chromatography, the crude products 17
were used in the reactions. Table 3 summarises the reaction
conditions and yields for the different Suzuki couplings.
Figure 5. a) ICl, Et2O, 1 h, 20 °C (X = I); b) 6-bromohex-1-ene
(15a), 6-iodohex-1-ene (15b), or 10-iododec-1-ene (15c), K2CO3,
KI, DMF, 18 h, 60 °C; c) dec-9-en-1-ol (15d), PPh3, diisopropyl
azodicarboxylate (DIAD), THF, 18 h, 20 °C; d) n-butyllithium,
THF, –78 °C, 1 h, then B(OMe)3, 2 h, warm to room temp., then
H2O, 10 min, e) hex-5-en-1-ol (15e), oct-7-en-1-ol (15f) or dec-9-en-
1-ol (15d), PPh3, diisopropyl azodicarboxylate (DIAD), THF, 18 h,
20 °C.
Table 1. Reaction conditions and yields for the ether formation to
give the alkenoxyarenes 16 and 19.
Figure 6. 2,9-Diaryl-1,10-phenanthrolines 21 and 22 were obtained
by Suzuki couplings of 2,9-diiodo-1,10-phenanthroline (12) with
phenylboronic acids 17 and 20.
Arene Alkene Reaction conditions
Product
% Yield
14b
14b
14b
14b
14a
14a
18
15a
15b
15c
15d
15c
15d
15e
15f
15d
K2CO3, KI, DMF, 18 h, 60 °C
K2CO3, DMF, 18 h, 60 °C
K2CO3, DMF, 18 h, 70 °C
PPh3, DIAD, THF, 18 h, 20 °C
K2CO3, DMF, 18 h, 70 °C
PPh3, DIAD, THF, 18 h, 20 °C
PPh3, DIAD, THF, 18 h, 20 °C
PPh3, DIAD, THF, 18 h, 20 °C
PPh3, DIAD, THF, 18 h, 20 °C
16a
16a
16b
16b
16c
16c
19a
19b
19c
75
65
71
22
98
76
71
87
79
The final steps in the syntheses of the concave 1,10-phen-
anthrolines 3 and 4 were ring-closing metathesis and hydro-
genation of the new double bonds of the ring (Figure 8).
The Grubbs catalyst (first generation) was used for ring-
closing metathesis, with the reactions being carried out at
room temperature.
18
18
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Concave 1,10-Phenanthrolines as Ligands for Cyclopropanations
Table 4. Yields for ring-closing metatheses (RCM) and subsequent
hydrogenations in the syntheses of 1,10-phenanthroline macro-
cycles 3 and 4.
21,
RCM
24,
RCM
Hydrogenation 3, 4 Hydrogenation
22 reaction
25
% yield
reaction time
% yield
time
21a
18 h
mixed
fractions
71
Figure 7. The monochloro-monoaryl-1,10-phenanthroline 23 could
be isolated as an intermediate when 2,9-dichloro-1,10-phenan-
throline (10) was used as starting material. In a subsequent Suzuki
coupling, 23 could be coupled with boronic acid 17b to give 21b.
a) Pd(PPh3)4, Ba(OH)2, dimethoxyethane/water, 17b, 40 h, room
temp.; b) Pd(PPh3)4, Ba(OH)2, dimethoxyethane/water, 17b, 18 h,
room temp.
21b
22a
22b
22c
18 h
14 d
48 h
18 h
24b
25a
25b
25c
18 h
3 d
4 d
3b
4a
4b
4c
95
44
60
58
53
87
35
18 h
1,10-Phenanthroline-Based Ligands in Cyclopropanations
The copper(I)-catalysed cyclopropanation of alkenes can
be carried out with different diazo compounds, of which
ethyl diazoacetate (26) is commercially available. This diazo
compound has usually been used to evaluate new catalysts.
In addition to cyclopropanes, diethyl fumarate (30) and
maleate (31) are usually detected as by-products (Figure 9).
Table 3. Yields of the Suzuki coupling reactions of 2,9-diiodo-1,10-
phenanthroline (12) with phenylboronic acids 17 and 20 to give
2,9-diaryl-1,10-phenanthrolines 21 and 22.
Boronic n, R
Reaction
Product
% Yield
acid
conditions
17a
17b
n = 4,
R = O(CH2)4CH=CH2
n = 8,
R = O(CH2)8CH=CH2
n = 4, R = H
n = 6, R = H
18 h, 60 °C
80 h, 80 °C
21a
21b
27
10,
(14[a]
30
)
20a
20b
20c
72 h, 80 °C
18 h, 80 °C
18 h, 80 °C
22a
22b
22c
46
80
n = 8, R = H
[a] Compound 21b was synthesised in a two-step reaction starting
from 10 instead of 12 with isolation of intermediate 23.
Figure 9. The copper(I) carbenoid 27 is the reactive intermediate
in the cyclopropanation of indene (28) with ethyl diazoacetate (26).
In addition to the cyclopropanes exo-29 and endo-29, diethyl fum-
arate (30) and diethyl maleate (31) are always found as by-products.
The macrocyclic 1,10-phenanthrolines 3 and 4 were
tested as ligands for copper(I) ions in the cyclopropanation
of indene (28). As reference, the copper(I) trifluoro-
methanesulfonate/benzene complex was used in the absence
of additional ligands. For this reaction, a diastereomeric ra-
tio of 32:68 (endo/exo) is reported.[8] Through the use of
1,10-phenanthroline ligands, this diastereoselectivity can be
changed[8,11,16,17,18] either towards exo or towards endo
products (see Introduction). Table 5 compares the selectivi-
Figure 8. Syntheses of 1,10-phenanthroline macrocycles 3 and 4
from the 2,9-diaryl-1,10-phenanthrolines 21 and 22.
After ring-closing metathesis, the new double bonds were ties of the new ligands 3 and 4 with those of other 1,10-
hydrogenated under hydrogen in the presence of palladium phenanthrolines in the copper(I)-catalysed cyclopropan-
on charcoal as heterogeneous catalyst. Table 4 summarises ation of indene (28). To allow better comparison of the
the yields for the ring-closing reactions and the hydrogena- endo/exo selectivities, all reactions were carried out as batch
tions.
reactions under inert atmosphere and identical conditions.
Eur. J. Org. Chem. 2009, 2328–2341
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F. Eggers, U. Lüning
FULL PAPER
cinol (14a, Acros Organics), n-butyllithium (2.5  in hexanes, Ald-
rich), copper(I) triflate hemibenzene complex (Aldrich), dec-9-en-
1-ol (15d, Merck), ethyl diazoacetate (26, Aldrich), 1,3-dibro-
mopropane (Fluka), 1,2-dichloroethane (Acros Organics), di-
isopropyl azodicarboxylate (DIAD, Fluka), 1,2-dimethoxyethane
(Aldrich), N,N-dimethylformamide (Fluka, Ն99.8%), dimethyl sul-
fate (Merck), n-hexadecane (Aldrich), hex-5-en-1-ol (15e, Alfa
Aesar), hypophosphoric acid (Riedel-de Haën), conc. hydroiodic
acid (Merck), imidazole (Fluka), indene (28, Fluka), iodine
(Merck), iodine monochloride (Lancaster), nitrobenzene (Merck),
palladium on charcoal (10%, Fluka), 1,10-phenanthroline (5,
Merck, ChemPur), phosphorus pentachloride (Fluka), phosphoryl
chloride (Merck), potassium carbonate (Merck), potassium hexa-
cyanoferrate(III) (Merck), potassium iodide (Merck), resorcinol
(13, Riedel-de Haën), sodium chloride (Merck), sodium hydride
(Aldrich, 60% dispersion in mineral oil), sodium hydroxide
(Merck), sodium thiosulfate pentahydrate (Fluka), tetrakis(tri-
phenylphosphane)palladium(0) (Merck, Acros Organics), trimethyl
borate (Fluka), triphenylphosphane (Fluka). 2,9-Dichloro-1,10-
phenanthroline (10) and 2,9-diiodo-1,10-phenanthroline (12) were
prepared by literature procedures.[20,21] Oct-7-en-1-ol (15f) was syn-
thesised by Dipl.-Chem. D. Stoltenberg by a literature procedure.[23]
Dry solvents were obtained with suitable desiccants: tetra-
hydrofuran was distilled from lithium aluminium hydride, diethyl
ether from sodium, and dichloromethane from calcium hydride.
Column chromatography was carried out on basic alumina (Fluka,
activity I) or silica gel (Macherey–Nagel, activity I). The prepara-
tive centrifugally accelerated thin-layer chromatograph (Chromato-
In synthetic applications, the yields of cyclopropanes can
be improved by slow addition of the diazoacetate, because
the amount of by-products 30 and 31 decreases with di-
lution.
Table 5. Results of the copper(I)-catalysed cyclopropanations of in-
dene (28) with ethyl diazoacetate (26) in the presence of a range of
1,10-phenanthrolines 3 and 4. For comparison with previous re-
sults, the yields and selectivities obtained with the phenanthroline-
bridged calix[6]arene 2a and the bimacrocyclic phenanthroline 1b
with bis-ortho-substituted bridgeheads with chain lengths of 10 car-
bon atoms are shown (n.m.: not measured).
Ligand
% Yield
29/(30 + 31)
endo-29/exo-29
31/30
No ligand
71/15
68/22
45/n.m.
46/14
15/3
70/16
66/13
26:74
1:99
76:24
32:68
46:54
30:70
26:74
38:62
n.m.
89:11
44:56
55:45
37:63
34:66
1b
2a
3b
4a
4b
4c
As documented in Table 5, the selectivities achieved in
the cyclopropanations of indene (28) lie between those
found for concave 2,9-diaryl-1,10-phenanthrolines (see 1b)
and for the calixarene derivatives (see 2a). As would be ex-
pected, the endo fractions have increased relative to 1 with
the changing of the chains from bis-ortho orientations to
ortho,para or to para only. In most cases, however, the influ-
ences of the ligands on the selectivities of the cyclopropana-
tions are small, leading to values comparable to those ob-
served with copper(I) alone. However on comparison of
compounds of varying ring size, a tendency towards greater
endo selectivity is observed with smaller rings. Conse-
quently, the next step in catalyst development should be to
minimise the number of atoms in the chains of the macro-
cyclic 1,10-phenanthrolines 3 and 4 in order to enhance
endo selectivities.
1
tron) was a model 7924T from Harrison Research. H NMR and
13C NMR spectra were recorded on Bruker AC 200 (200 MHz),
ARX 300 (300 MHz or 75 MHz), DRX 500 (500 MHz or
125 MHz) or Avance 600 (600 MHz or 150 MHz) instruments, with
tetramethylsilane as internal standard. IR spectra were measured
on a Perkin–Elmer 1600 Series device. MS spectra were recorded
on a Finnigan MAT 8230 or MAT 8200 machine or on an Applied
Biosystems Mariner ESI-TOF MS 5280. Elemental analyses were
carried out on a EuroVector instrument. Gas chromatography was
performed with 6890 N (Agilent); split/splitless injector, split ratio
11:1, injector temp. 240 °C, FID detector temp. 250 °C.
2,21,23,42-Tetraoxa-1,22(1,3,4)-dibenzena-43(2,9)-1,10-phen-
anthrolina-bicyclo[20.20.1]tritetracontaphane
(3b):
Palladium
Conclusions
(12 mg, 10% on activated charcoal) was suspended in acid-free
ethyl acetate (2 mL). Under hydrogen, 2,21,23,42-tetraoxa-
1,22(1,3,4)-dibenzena-43(2,9)-1,10-phenanthrolina-bicyclo-
[20.20.1]tritetracontaphan-11,32-diene (24b, 23 mg, 26 µmol), dis-
solved in acid-free ethyl acetate (3 mL), was added. The reaction
mixture was stirred under hydrogen at room temp. for 16 h. The
suspension was filtered through a layer of basic aluminium oxide
(dichloromethane). Evaporation of the solvent in vacuo yielded a
light yellow oil (22 mg, 25 µmol, 95%). 1H NMR (500 MHz,
CDCl3): δ = 0.82–1.15 (m, 16 H, CH2), 1.21–1.53 (m, 40 H, CH2),
We have shown that different macrocyclic (4) and bi-
macrocyclic (3) 1,10-phenanthrolines with new geometries
could be synthesised in acceptable to good yields. These
1,10-phenanthrolines 3 and 4 were used as ligands for cop-
per(I), and the resulting complexes were tested in the cyclo-
propanation of indene (28) with ethyl diazoacetate (26).
Unfortunately, the influences of the ligands on the exo/endo
stereoselectivities were small but the ring size dependence
indicates that higher selectivities might be expected for
macrocycles with smaller ring sizes.
3
1.84 (mc, 8 H, OCH2CH2), 4.03 (t, J ≈ 6.9 Hz, 4 H, OCH2), 4.04
3
4
(t, J = 6.7 Hz, 4 H, OCH2), 6.56 (d, J = 2.3 Hz, 2 H, 2-CArH),
6.76 (dd, 3J = 8.6, 4J = 2.3 Hz, 2 H, 6-CArH), 7.73 (s, 2 H, 5,6-
CPhenH), 8.16 (d, 3J = 8.4 Hz, 2 H, 4,7-CPhenH), 8.29 (d, 3J =
3
8.4 Hz, 2 H, 3,8-CPhenH), 8.35 (d, J = 8.6 Hz, 2 H, 5-CArH) ppm.
Experimental Section
13C NMR (125 MHz, CDCl3): δ = 25.7, 25.8, 26.1, 26.2, 28.2, 28.7,
29.1, 29.4, 29.5 (d, CH2), 68.2, 68.8 (d, OCH2), 100.3 (d, 2-CAr),
106.5 (d, 6-CAr), 123.2 (s, 1-CAr), 124.3 (d, 3,8-CPhen), 124.8 (d, 5,6-
CPhen), 125.5 (d, 5-CAr), 127.0 (s, 4a,6a-CPhen), 133.3 (d, 4,7-CPhen),
146.1 (s, 10a,10b-CPhen), 156.2 (s, 2,9-CPhen), 158.3 (s, 3-CAr), 161.2
General Remarks: The following chemicals were obtained commer-
cially and were used without further purification: acetic acid
(Merck), ammonia (Biesterfeld), barium hydroxide octahydrate
(Merck),
benzylidenebis(tricyclohexylphosphane)dichlororuthe-
nium (Grubbs type I catalyst, Aldrich), 6-bromohex-1-ene (15a,
Acros Organics), 4-bromophenol (18, Alfa Aesar), 4-bromoresor-
(s, 4-CAr) ppm. IR (KBr): ν = 2924, 2852 (aliph. CH), 1609, 1580,
˜
1487 (arom. C=C), 1278, 1181, 1024 (COC) cm–1. MS (EI, 70 eV):
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© 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 2009, 2328–2341

Concave 1,10-Phenanthrolines as Ligands for Cyclopropanations
m/z (%) = 896 (28) [M]+, 813 (36) [M – C6H13]+, 799 (100) [M – coal (6 mg, 10%) in acid-free ethyl acetate (2 mL) and 4,23-dioxa-
C7H13]+, 785 (97) [M – C8H15]+, 771 (82) [M – C9H17]+, 645 (61) 1,3(1,4)-dibenzena-2(2,9)-1,10-phenanthrolina-cyclotricosaphan-
[M – C18H35]+. MS (ESI, CHCl3/MeOH): m/z (%) = 897.6 (100) [M
11-ene (25c, 35 mg, 57 µmol) in acid-free ethyl acetate (3 mL) with
+ H]+, 883.5 (72) [M + H – CH2]+. HR-MS (ESI, CHCl3/MeOH): stirring for 16 h to yield yellow crystals (20 mg, 33 µmol, 58%). 1H
C60H84N2O4 (896.64). calcd. for C60H84N2O4 + H+: 897.6504; NMR (100 MHz, CDCl3): δ = 1.24–1.43 (m, 24 H, CH2), 1.52 (mc,
found 897.6585 (∆ = 9.0 ppm), calcd. for C5913CH84N2O4 + H+: 4 H, OCH2CH2CH2), 1.86 (mc, 4 H, OCH2CH2), 4.08 (t, 3J =
898.6537; found 898.6613 (∆ = 8.5 ppm).
3
6.6 Hz, 4 H, OCH2), 7.11 (mc with d, J = 8.8 Hz, 4 H, 3,5-CArH),
3
7.71 (s, 2 H, 5,6-CPhenH), 8.06 (d, J = 8.4 Hz, 2 H, 3,8-CPhenH),
4,15-Dioxa-1,3(1,4)-dibenzena-2(2,9)-1,10-phenanthrolina-cyclo-
pentadecaphane (4a): Palladium on charcoal (10 mg, 10%) was sus-
pended in acid-free ethyl acetate (2 mL) under hydrogen. 4,15-Di-
oxa-1,3(1,4)-dibenzena-2(2,9)-1,10-phenanthrolina-cyclopenta-
decaphan-7-ene (25a, 45 mg, 90 µmol) was dissolved in acid-free
ethyl acetate (5 mL) and added to the suspension. Under hydrogen,
the mixture was stirred at room temp. for 3 d before filtration
through basic aluminium oxide (dichloromethane). Evaporation of
the solvent in vacuo yielded colourless crystals (20 mg, 40 µmol,
44%); m.p. 234–236 °C. 1H NMR (600 MHz, CDCl3): δ = 1.34–
1.54 (m, 12 H, CH2), 1.84 (mc, 4 H, OCH2CH2), 4.09 (t, 3J =
8.2 (d, 3J = 8.4 Hz, 2 H, 4,7-CPhenH), 8.43 (mc with d, 3J = 8.9 Hz,
4 H, 2,6-CArH) ppm. 13C NMR (150 MHz, CDCl3): δ = 25.9, 26.1,
29.1, 29.2, 29.50, 29.55, 29.6 (t, CH2), 29.8 (t, OCH2CH2), 68.2 (t,
OCH2), 114.8 (d, 3,5-CAr), 119.2 (d, 3,8-CPhen), 125.5 (d, 5,6-CPhen),
127.5 (s, 4a,6a-CPhen), 129.0 (d, 2,6-CAr), 132.0 (s, 1-CAr), 136.7 (d,
4,7-CPhen), 146.1 (s, 10a,10b-CPhen), 156.4 (s, 2,9-CPhen), 160.6 (s,
4-CAr) ppm. IR (KBr): ν = 2928 (aliph. CH), 1607, 1583, 1491
˜
(arom. C=C), 1250, 1024 (C–O–C), 833 (1,4-disubst. ben-
zene) cm–1. MS (ESI, CHCl3/MeOH): m/z (%) = 615 (100) [M +
H]+. MS (EI, 70 eV): m/z (%) = 614 (71) [M]+, 364 (100)
[C24H16N2O2]+. HR-MS (EI, 70 eV): calcd. for C42H50N2O2:
3
6.6 Hz, 4 H, OCH2), 7.09 (mc with d, J = 8.8 Hz, 4 H, 3,5-CArH),
614.3872; found 614.3867 (∆
=
0.8 ppm), calcd. for
3
7.71 (s, 2 H, 5,6-CPhenH), 8.03 (d, J = 8.4 Hz, 2 H, 3,8-CPhenH),
C4113CH50N2O2: 615.3906; found 615.3903 (∆ = 0.4 ppm).
8.23 (d, 3J = 8.4 Hz, 2 H, 4,7-CPhenH), 8.36 (mc, 4 H, 2,6-
C
ArH) ppm. 13C NMR (150 MHz, CDCl3): δ = 25.7, 27.6, 29.3 (t,
4-Iodoresorcinol (14b): This compound was synthesised by a litera-
CH2), 31.6 (t, OCH2CH2), 67.4 (t, OCH2), 114.8 (d, 3,5-CAr), 119.3 ture procedure[24] from iodine monochloride (8.00 g, 50.0 mmol)
(d, 3,8-CPhen), 125.5 (d, 5,6-CPhen), 127.5 (s, 4a,6a-CPhen), 129.0 (d,
2,6-CAr), 132.0 (s, 1-CAr), 136.6 (d, 4,7-CPhen), 146.0 (s, 10a,10b-
and resorcinol (13, 5.50 g, 50.0 mmol) in dry diethyl ether (50 mL)
to yield colourless crystals (4.71 g, 19.9 mmol, 40%), ref.[24] 70%;
1
CPhen), 156.5 (s, 2,9-CPhen), 160.6 (s, 4-CAr) ppm. IR (KBr): ν = m.p. 67–71 °C, ref.[25] 67–70 °C. H NMR (300 MHz, CDCl3): δ =
˜
3
2963 (aliph. CH), 1604, 1481 (arom. C=C), 1261, 1095 (C–O–C), 4.94 (brs, 1 H, 1-CArOH), 5.26 (brs, 1 H, 3-CArOH), 6.27 (dd, J
802 (1,4-disubst. benzene) cm–1. MS (EI, 70 eV): m/z (%) = 502
(100) [M]+, 448 (16) [C30H28N2O2]+, 364 (79) [C24H26N2O2]+. MS
(CI, isobutane): m/z (%) = 503 (100) [M]+. MS (ESI, CHCl3/
= 8.6, 4J = 2.7 Hz, 1 H, 6-CArH), 6.54 (d, 4J = 2.9 Hz, 1 H, 2-
3
C
ArH), 7.46 (d, J = 8.6 Hz, 1 H, 5-CArH) ppm. MS (EI, 70 eV):
m/z (%) = 236 (100) [M]+, 109 (12) [M – I]+. MS (CI, isobutane):
MeOH): m/z (%) = 503 (100) [M + H]+. HR-MS (EI, 70 eV): calcd. m/z (%) = 237 (100) [M + H]+, 236 (83) [M]+, 110 (16) [M – I]+.
for C34H34N2O2: 502.2620; found 502.2616 (∆ = 0.9 ppm), calcd.
1-Iodohex-5-ene (15b): This compound was synthesised by a litera-
for C3313CH34N2O2: 503.2654; found 503.2653 (∆ = 0.2 ppm).
ture procedure[26] from hex-5-en-1-ol (15e, 7.10 mL, 5.95 g,
4,19-Dioxa-1,3(1,4)-dibenzena-2(2,9)-1,10-phenanthrolina-cyclo-
nonadecaphane (4b): This compound was synthesised by the pro-
cedure described above for 4,15-dioxa-1,3(1,4)-dibenzena-2(2,9)-
1,10-phenanthrolina-cyclopentadecaphane (4a) with palladium on
charcoal (10 mg, 10%) in acid-free ethyl acetate (3 mL) and 4,19-
dioxa-1,3(1,4)-dibenzena-2(2,9)-1,10-phenanthrolina-cyclonona-
decaphan-9-ene (25b, 25 mg, 45 µmol) in acid-free ethyl acetate
(3 mL) with stirring for 18 h to yield yellow crystals (15 mg,
59.2 mmol) with triphenylphosphane (21.7 g, 83.0 mmol), imid-
azole (5.65 g, 83.0 mmol), and iodine (21.0 g, 83.0 mmol) in dry
dichloromethane (180 mL) to yield a colourless liquid (11.4 g,
54.5 mmol, 92%), ref.[26] 90%. n2D0 = 1.5105, ref.[26] 1.5106. 1H
NMR (300 MHz, CDCl3): δ = 1.52 (mc, 2 H, CH2CH2CH=), 1.84
3
3
4
[mc, 2 H, CH2(CH2)2I], 2.08 (dtt, Jt = 7.3, Jd = 6.8, Jt = 1.4 Hz,
3
3
2 H, CH2CH=), 3.20 (t, J = 7.0 Hz, 2 H, CH2I), 4.97 (ddt, Jd =
2
4
3
10.0, Jd = 2.0, Jt = 1.2 Hz, 1 H, CH=CHHcis), 5.02 (ddt, Jd
=
27 µmol, 60%). 1H NMR (600 MHz, CDCl3): δ = 1.27–1.45 (m, 16 17.0, Jd = 2.0, Jt = 1.5 Hz, 1 H, CH=CHHtrans), 5.79 (ddt, Jt =
2
4
3
3
3
H, CH2), 1.50 (mc, 4 H, CH2), 1.85 (mc, 4 H, OCH2CH2), 4.15 (mc
17.0, Jt = 10.2, Jt = 6.7 Hz, 1 H, =CH) ppm.
with t, 3J = 7.1 Hz, 4 H, OCH2), 7.11 (mc, 4 H, 3,5-CArH), 7.73 (s,
1-Iododec-9-ene (15c): This compound was synthesised by the lit-
erature procedure for 1-iodohex-5-ene[26] with triphenylphosphane
(21.7 g, 83.0 mmol) and imidazole (5.65 g, 83 mmol) in dry dichlo-
romethane (180 mL), with iodine (21.0 g, 83.0 mmol), dec-9-en-1-
ol (15d, 10.5 mL, 9.24 g, 59.2 mmol) and sodium thiosulfate penta-
hydrate (18.5 g, 74.7 mmol). After workup as described for 1-
iodohex-5-ene (15b, see above), the solvent was evaporated in vacuo
and the residue was dissolved in dichloromethane (ca. 5 mL). After
addition of petroleum ether (b.p. 30–60 °C, ca. 200 mL) the mixture
was filtered through silica gel and the solvent was evaporated to
yield a colourless liquid (10.9 g, 40.9 mmol, 69%). 1H NMR
(200 MHz, CDCl3): δ = 1.24–1.42 (m, 10 H, CH2), 1.82 (mc, 2 H,
CH2CH2I), 2.04 (mc, 2 H, CH2CH=), 3.19 (t, 3J = 7.0 Hz, 2 H,
ICH2), 4.93 (ddt, 3Jd = 10.2, 2Jd = 2.2, 4Jt = 1.2 Hz, 1 H,
3
2 H, 5,6-CPhenH), 8.05 (d, J = 8.3 Hz, 2 H, 3,8-CPhenH), 8.24 (d,
3
3J = 8.4 Hz, 2 H, 4,7-CPhenH), 8.42 (mc with d, J = 8.8 Hz, 4 H,
2,6-CArH) ppm. 13C NMR (150 MHz, CDCl3): δ = 25.8, 25.9, 28.5,
28.9, 29.3, 29.3, 29.7 (t, CH2), 30.1 (t, OCH2CH2), 68.3 (t, OCH2),
115.2 (d, 3,5-CAr), 119.3 (d, 3,8-CPhen), 125.5 (d, 5,6-CPhen), 127.4
(s, 4a,6a-CPhen), 129.2 (d, 2,6-CAr), 130.4 (s, 1-CAr), 136.6 (d, 4,7-
CPhen), 146.1 (s, 10a,10b-CPhen), 156.4 (s, 2,9-CPhen), 160.3 (s, 4-
CAr) ppm. IR (KBr): ν = 2924 (aliph. CH), 1605, 1488 (arom.
˜
C=C), 1249, 1173 (C–O–C), 835 (1,4-disubst. benzene) cm–1. MS
(ESI, CHCl3/MeOH): m/z (%) = 559 (75) [M + H]+. MS (EI,
70 eV): m/z (%) = 558 (58) [M]+, 364 (100) [C24H14N2O2]+. HR-
MS (EI, 70 eV): calcd. for C38H42N2O2: 558.3247; found 558.3246
(∆
=
0.1 ppm), calcd. for C3713CH42N2O2: 559.3280; found
559.3229 (∆ = 9.2 ppm).
3
2
4
CH=CHHcis), 5.00 (ddt, Jd = 17.1, Jd = 2.2, Jt = 1.6 Hz, 1 H,
3
3
3
4,23-Dioxa-1,3(1,4)-dibenzena-2(2,9)-1,10-phenanthrolina-cyclo-
tricosaphane (4c): This compound was synthesised by the procedure
CH=CHHtrans), 5.81 (ddt, Jt = 17.1, Jt = 10.2, Jt = 6.7 Hz, 1 H,
=CH) ppm. 13C NMR (50 MHz, CDCl3): δ = 7.3, 28.5, 28.8, 29.0,
described above for 4,15-dioxa-1,3(1,4)-dibenzena-2(2,9)-1,10- 29.3, 30.5, 33.6, 33.8 (t, CH2), 114.2 (t, CH2=), 139.1 (d,
phenanthrolina-cyclopentadecaphane (4a) with palladium on char- CH=) ppm. IR (neat): ν = 2925, 2852 (aliph. CH), 1640 (C=C),
˜
Eur. J. Org. Chem. 2009, 2328–2341
© 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
2333

F. Eggers, U. Lüning
1460 (arom. C=C), 994, 909 (monosubst. alkene), 599 (I–C) cm–1. the suspension was heated to 70 °C under nitrogen for 16 h. After
FULL PAPER
MS (EI, 70 eV): m/z (%) = 266 (100) [M]+. MS (CI, isobutane): m/z
(%) = 267 (50) [M + H]+, 139 (23) [M – I]+, 111 (80) [C8H15]+, 99
(100) [C7H15]+. HR-MS (EI, 70 eV): calcd. for C10H19I: 266.0532;
found 266.0532 (∆ = 0.3 ppm), calcd. for C913CH19I: 267.0565;
found 267.0536 (∆ = 10.9 ppm). C10H19I (266.05): calcd. C 45.13,
H 7.20; found C 44.83, H 7.26.
the system had cooled to room temp., sodium hydroxide solution
(2 ) and diethyl ether (25 mL each) were added and the layers
were separated. The water layer was extracted with diethyl ether
(3ϫ20 mL). The combined organic layer was washed twice with
sodium hydroxide solution (2 ) and brine (20 mL each) and dried
with magnesium sulfate. The solvent was evaporated and the crude
product was purified by column chromatography (silica gel, cyclo-
hexane/ethyl acetate, 9:1, Rf = 0.67) to yield 1.16 g of a colourless
liquid (2.27 mmol, 71%).
2,4-Bis(hex-5-enyloxy)-1-iodobenzene (16a). Method A: 4-Iodore-
sorcinol (14b, 1.69 g, 7.17 mmol) was dissolved in dry N,N-dimeth-
ylformamide (24 mL) and, after addition of potassium carbonate
(5.96 g, 43.0 mmol), potassium iodide (480 mg, 2.90 mmol) and 6-
bromohex-1-ene (15a, 2.44 mL, 2.92 g, 17.9 mmol), was stirred at
60 °C under nitrogen for 18 h. The solvent was evaporated in
vacuo, and the residue was dissolved in sodium hydroxide solution
(2 ) and diethyl ether (25 mL each). After separation of the layers,
the water layer was extracted with diethyl ether (3ϫ20 mL). The
combined organic layer was washed with sodium hydroxide solu-
tion (2 , 3ϫ20 mL) and brine (20 mL). After drying with magne-
sium sulfate, the solvent was evaporated in vacuo and the crude
product was purified by column chromatography (silica, cyclohex-
ane/ethyl acetate, 15:1, Rf = 0.74) to yield a colourless liquid
(2.11 g, 5.40 mmol, 75%).
Method B: 4-Iodoresorcinol (14b, 1.50 g, 6.36 mmol), tri-
phenylphosphane (3.34 g, 12.7 mmol), and dec-9-en-1-ol (15d,
3.53 mL, 2.99 g, 19.1 mmol) were dissolved in dry tetrahydrofuran
(35 mL) and cooled to 0 °C. Under nitrogen, diisopropyl azodicar-
boxylate (DIAD, 3.74 mL, 19.1 mmol) was slowly added and the
solution was afterwards stirred at room temp. for 18 h. The reac-
tion mixture was hydrolysed with water (20 mL) and sodium hy-
droxide solution (2 , 4.7 mL). After the system had been stirred
for 30 min and the layers separated, the water layer was extracted
with diethyl ether (3ϫ20 mL). The combined organic layer was
washed once with brine (20 mL) and dried with magnesium sulfate.
The solvent was evaporated and the crude product was purified by
column chromatography (silica gel, cyclohexane/ethyl acetate, 9:1,
Rf ≈ 0.70) to yield a colourless liquid (705 mg, 1.38 mmol, 22%).
1H NMR (600 MHz, CDCl3): δ = 1.29–1.41 (m, 12 H, CH2), 1.41–
1.47 (m, 2 H, CH2), 1.51 (mc, 2 H, CH2), 1.76 (mc, 2 H,
OCH2CH2), 1.82 (mc, 2 H, OCH2CH2), 2.04 (mc, 4 H, CH2CH=),
3.91 (t, 3J = 6.6 Hz, 2 H, OCH2), 3.96 (t, 3J = 6.5 Hz, 2 H, OCH2),
Method B: 4-Iodoresorcinol (14b, 490 mg, 2.08 mmol) was dis-
solved in dry N,N-dimethylformamide (7 mL). After addition of
potassium carbonate (1.72 g, 12.4 mmol) and 6-iodohex-1-ene (15b,
1.08 g, 5.18 mmol), the suspension was stirred at 60 °C under nitro-
gen for 18 h. After evaporation of the solvent in vacuo, the residue
was dissolved in diethyl ether and sodium hydroxide solution (2 ,
20 mL each). The layers were separated and the water layer was
extracted with diethyl ether (3ϫ15 mL). The combined organic
layer was washed with sodium hydroxide solution (2 , 3ϫ15 mL)
and brine (15 mL) and dried with magnesium sulfate. After evapo-
ration of the solvent in vacuo, the crude product was purified by
column chromatography (silica gel, cyclohexane/ethyl acetate, 12:1,
Rf = 0.71) to yield a colourless liquid (539 mg, 1.35 mmol, 65%).
1H NMR (500 MHz, CDCl3): δ = 1.56 (quin, 3J = 7.5 Hz, 2 H,
3
2
4
4.93 (ddt, Jd = 10.2, Jd = 2.0, Jt = 1.2 Hz, 2 H, CH=CHHcis),
3
2
4
4.99 (ddt, Jd = 17.1, Jd = 1.9, Jt = 1.6 Hz, 2 H, CH=CHHtrans),
5.81 (ddt, 3Jt = 17.0, 3Jt = 10.2, Jt = 6.7 Hz, 2 H, =CH), 6.28 (dd,
3
3J = 8.6, J = 2.6 Hz, 1 H, 5-CArH), 6.39 (d, J = 2.6 Hz, 1 H, 3-
CArH), 7.58 (d, 3J = 8.6 Hz, 1 H, 6-CArH) ppm. 13C NMR
(150 MHz, CDCl3): δ = 26.0, 28.9, 29.1, 29.2, 29.3, 29.4 (t, CH2),
33.8 (t, CH2CH=), 68.3 (t, 4-CArOCH2), 69.2 (t, 2-CArOCH2), 75.4
(s, 1-CAr), 100.7 (d, 3-CAr), 107.7 (d, 5-CAr), 114.2 (t, =CH2), 139.0
(d, =CH), 139.2 (d, 6-CAr), 158.5 (s, 2-CAr), 160.9 (s, 4-CAr) ppm.
4
4
3
CH2CH2CH=), 1.63 (quin, J = 7.5 Hz, 2 H, CH2CH2CH=), 1.78
IR (neat): ν = 3074 (arom. CH), 2936 (aliph. CH), 1576, 1464
˜
(quin, 3J ≈ 7 Hz, 2 H, CH2CH2O), 1.84 (quin, 3J ≈ 7 Hz, 2 H,
(arom. C=C), 1302, 1186, 1041 (COC) cm–1. MS (EI, 70 eV): m/z
(%) = 512 (62) [M]+, 385 (8) [M – I]+, 236 (100) [C6H5IO2]+. MS
(CI, isobutane): m/z (%) = 513 (100) [M + H]+, 386 (41) [M +
H – I]+. HR-MS (EI, 70 eV): calcd. for C26H41IO2: 512.2152; found
512.2109 (∆ = 8.4 ppm), calcd. for C2513CH41IO2: 513.2185; found
513.2183 (∆ = 0.5 ppm). C26H41IO2 (512.22): calcd. C 60.93, H
8.06. C26H41IO2·0.7CH2Cl2 (512.22 + 67.84): calcd. C 56.07, H
7.47; found C 56.17, H 7.68.
3
4
CH2CH2O), 2.12 (dtt, Jd,t ≈ 7, Jt = 1.3 Hz, 2 H, CH2CH=), 2.15
3
4
3
(dtt, Jd,t ≈ 7, Jt = 1.3 Hz, 2 H, CH2CH=), 3.93 (t, J = 6.4 Hz, 2
H, OCH2), 3.98 (t, J = 6.4 Hz, 2 H, OCH2), 4.98 (ddt, 3Jd = 10.3,
3
2Jd = 1.8, Jt = 1.1 Hz, 2 H, =CHHcis), 5.04 (ddt, Jd = 17.2, Jd
4
3
2
4
3
3
= 2.0, Jt = 1.6 Hz, 2 H, =CHHtrans), 5.83 (ddt, Jd = 17.0, Jd
=
3
3
4
10.2, Jt = 6.6 Hz, 2 H, =CH), 6.29 (dd, J = 8.6, J = 2.7 Hz, 1
H, 5-CArH), 6.39 (d, 4J = 2.7 Hz, 1 H, 3-CArH), 7.59 (d, 3J =
8.6 Hz, 1 H, 6-CArH) ppm. 13C NMR (75 MHz, CDCl3): δ = 25.3,
25.4 (t, CH2CH2CH=), 28.5, 28.7 (t, OCH2CH2), 33.3, 33.4 (t,
CH2CH=), 68.0 (t, 4-CArOCH2), 68.9 (t, 2-CArOCH2), 75.3 (s, 1-
1-Bromo-2,4-bis(dec-9-enyloxy)benzene (16c). Method A: 4-Bromo-
resorcinol (14a, 1.84 g, 9.75 mmol) was dissolved in dry N,N-di-
CAr), 100.6 (d, 3-CAr), 107.6 (d, 5-CAr), 114.7, 114.8 (t, =CH2), methylformamide (40 mL). Addition of 10-iododec-1-ene (15c,
138.4, 138.6 (d, =CH), 139.0 (d, 6-CAr), 158.3 (s, 4-CAr), 160.8 (s,
6.44 g, 24.2 mmol) and potassium carbonate (8.07 g, 58.1 mmol)
was followed by stirring at 60 °C under nitrogen for 16 h. After the
system had cooled to room temp., the residue was dissolved in so-
dium hydroxide solution (2 ) and diethyl ether (25 mL each). The
layers were separated and the water layer was extracted with diethyl
ether (3ϫ20 mL). The combined organic layer was washed with
sodium hydroxide solution (2 , 2ϫ20 mL) and brine (20 mL) and
dried with magnesium sulfate. After evaporation of the solvent in
vacuo, the crude product was purified by column chromatography
(silica gel, cyclohexane/ethyl acetate, 9:1, Rf ≈ 0.80) to yield a
colourless liquid (4.49 g, 9.68 mmol, 98%).
2-CAr) ppm. IR (neat): ν = 3074 (arom. CH), 2935, 2869 (aliph.
˜
CH), 1639 (C=C), 1589, 1465, (arom. C=C), 1256, 1184
(COC) cm–1. MS (EI, 70 eV): m/z (%) = 400 (34) [M]+, 273 (15)
[M – I]+, 236 (100) [C6H5IO2]+, 110 (40) [C6H6O2]+. MS (CI, isobu-
tane): m/z (%) = 401 (100) [M + H]+, 330 (25), 316 (25), 274 (19)
[M + H – I]+, 83 (20) [C6H11]+. C18H25IO2 (400.09): calcd. C 54.01,
H 6.29. C18H25IO2·0.15C6H12 (400.09 + 12.62): calcd. C 54.97, H
6.54; found C 55.10, H 6.54.
2,4-Bis(dec-9-enyloxy)-1-iodobenzene (16b). Method A: 4-Iodore-
sorcinol (14b, 751 mg, 13.2 mmol) was dissolved in dry N,N-di-
methylformamide (15 mL). After addition of potassium carbonate
(2.64 g, 19.0 mmol) and 10-iododec-1-ene (15c, 2.11 g, 7.93 mmol),
Method B: 4-Bromoresorcinol (14a, 1.80 g, 9.54 mmol), dec-9-en-1-
ol (15d, 5.29 mL, 4.48 g, 28.6 mmol), and triphenylphosphane
2334
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© 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 2009, 2328–2341

Concave 1,10-Phenanthrolines as Ligands for Cyclopropanations
(5.01 g, 19.1 mmol) were dissolved in dry tetrahydrofuran (50 mL) 2.2 Hz, 2 H, 4,6-CArH), 7.15 (t, 3J = 8.0 Hz, 1 H, 5-CArH) ppm.
and cooled to 0 °C under nitrogen. Diisopropyl azodicarboxylate
(5.61 mL, 28.6 mmol) was added by syringe and the mixture was OCH2CH2), 33 (t, CH2CH=), 68 (t, OCH2), 102 (d, 2-CAr), 107 (d,
13C NMR (75 MHz, CDCl3): δ = 25 (t, CH2CH2CH=), 29 (t,
stirred at room temp. for 18 h. After hydrolysis with water (30 mL)
4,6-CAr), 115 (t, =CH2), 130 (d, 5-CAr), 139 (d, =CH), 160 (s, 1,3-
CAr) ppm. IR (neat): ν = 3075 (arom. CH), 2937, 2868 (aliph. CH),
and sodium hydroxide solution (2 , 7.0 mL) and stirring for
˜
30 min, the layers were separated and the water layer was extracted 1640 (C=C), 1589, 1469, (arom. C=C), 1263, 1182 (COC) cm–1.
with diethyl ether (3ϫ25 mL). The combined organic layer was
washed with brine (25 mL) and dried with magnesium sulfate. After
evaporation of the solvent in vacuo, the crude product was purified
by column chromatography (silica gel, cyclohexane/ethyl acetate,
9:1, Rf ≈ 0.80) to yield a colourless liquid (3.35 g, 7.22 mmol, 76%).
1H NMR (600 MHz, CDCl3): δ = 1.29–1.52 (m, 20 H, CH2), 1.76
(mc, 2 H, OCH2CH2), 1.82 (mc, 2 H, OCH2CH2), 2.04 (mc, 4 H,
MS (EI, 70 eV): m/z (%) = 275 (6) [M + H]+, 274 (28) [M]+, 193
(16) [C12H16O2 + H]+, 110 (100) [C6H6O2]+. MS (CI, isobutane):
m/z (%) = 275 (100) [M + H]+, 274 (12) [M]+. C18H26O2 (274.19):
calcd. C 78.79, H 9.55. C18H26O2·0.2CH2Cl2 (274.19 + 19.38):
calcd. C 74.14, H 9.04; found C 73.99, H 9.28.
2,4-Bis(dec-9-enyloxy)phenylboronic Acid (17b). Method A: 2,4-
Bis(dec-9-enyloxy)-1-iodobenzene (16b, 600 mg, 1.17 mmol) was
dissolved in dry tetrahydrofuran (10 mL) and cooled to –78 °C un-
der nitrogen. After addition of n-butyllithium (0.54 mL,
1.34 mmol, 2.5  in hexanes) and stirring at –78 °C for 1 h, tri-
methyl borate (0.41 mL, 4.2 mmol) was added. The solution was
warmed to room temp. during 2 h before hydrolysis was carried out
with water (20 mL). After separation of the layers, the water layer
was extracted with diethyl ether (3ϫ20 mL). The combined or-
ganic layer was washed with brine (20 mL) and dried with magne-
sium sulfate. Evaporation of the solvents in vacuo yielded the yel-
low crystalline crude product (514 mg).
3
3
CH2CH=), 3.91 (t, J = 6.6 Hz, 2 H, OCH2), 3.98 (t, J = 6.5 Hz,
2 H, OCH2), 4.93 (ddt, 3Jd = 10.2, 2Jd = 2.1, 4Jt = 1.3 Hz, 2 H,
3
2
4
CH=CHHcis), 4.99 (ddt, Jd = 17.1, Jd = 2.1, Jt = 1.6 Hz, 2 H,
CH=CHHtrans), 5.81 (ddt, 3Jt = 17.0, Jt = 10.2, Jt = 6.7 Hz, 2 H,
3
3
3
4
4
=CH), 6.36 (dd, J = 8.7, J = 2.7 Hz, 1 H, 5-CArH), 6.46 (d, J =
2.7 Hz, 1 H, 3-CArH), 7.37 (d, 3J = 8.7 Hz, 1 H, 6-CArH) ppm. 13
C
NMR (150 MHz, CDCl3): δ = 26.0 (2ϫt, CH2), 28.9 (2ϫt, CH2),
29.1, 29.3 (2ϫt, CH2), 29.4 (2ϫt, CH2), 33.8 (2ϫt, CH2CH=),
68.4 (t, 4-CArOCH2), 69.2 (t, 2-CArOCH2), 101.6 (d, 3-CAr), 102.9
(s, 4-CAr), 106.6 (d, 5-CAr), 114.2 (2ϫt, =CH2), 133.0 (d, =CH),
139.2 (d, 6-CAr), 156.2 (s, 2-CAr), 159.7 (s, 1-CAr) ppm. IR (neat):
ν = 3075 (arom. CH), 2925 (aliph. CH), 1595, 1466 (arom. C=C),
˜
Method B: 1-Bromo-2,4-bis(dec-9-enyloxy)benzene (16c, 3.01 g,
6.50 mmol) was dissolved under nitrogen in dry tetrahydrofuran
(55 mL) and cooled to –78 °C. Addition of n-butyllithium (3.0 mL,
7.4 mmol, 2.5  in hexanes) was followed by stirring at –78 °C for
1 h. Trimethyl borate (2.28 mL, 23.0 mmol) was added and the
solution was warmed to room temp. while stirring for 2 h. After
addition of water (20 mL) and separation of the layers, the water
layer was extracted with diethyl ether (3ϫ25 mL). The combined
organic layer was washed with brine (30 mL) and dried with mag-
nesium sulfate. Evaporation of the solvent in vacuo yielded the
1306, 1187 (COC) cm–1. MS (EI, 70 eV): m/z (%) = 466, 464 (64,
61) [M]+, 328, 326 (10, 11) [M – C10H18]+, 190, 188 (100, 100)
[C6H5BrO2]+. MS (CI, isobutane): m/z (%) = 467, 465 (100, 99) [M
+ H]+, 329, 327 (11, 11) [M – C10H18]+, 190, 188 (51, 55)
[C6H5BrO2]+. C26H41BrO2 (464.23): calcd. C 67.08, H 8.88.
C26H41BrO2·0.1C6H12 (464.23 + 8.41): calcd. C 67.41, H 8.98;
found C 67.45, H 9.06.
2,4-Bis(hex-5-enyloxy)phenylboronic Acid (17a): 2,4-Bis(hex-5-en-
yloxy)-1-iodobenzene (16a, 200 mg, 500 µmol) was dissolved in dry
tetrahydrofuran (10 mL) and cooled to –78 °C before addition of
n-butyllithium (0.22 mL, 0.55 mmol, 2.6  in hexanes) and stirring
at –78 °C for 1 h. After addition of trimethyl borate (0.18 mL,
1.7 mmol), the solution was stirred for 2 h and warmed to room
temp. The reaction was hydrolysed with water (20 mL). The layers
were separated and the water layer was extracted with diethyl ether
(3ϫ20 mL). The combined organic layer was washed once with
brine (20 mL) and dried with magnesium sulfate. The solvent was
evaporated to yield a colourless liquid (153 mg) as crude product.
1H NMR (200 MHz, CDCl3): δ = 1.58 (mc, 4 H, CH2CH2CH=),
1.72–1.87 (m, 4 H, CH2CH2O), 2.13 (mc, 4 H, CH2CH=), 3.95 (t,
1
colourless crystalline crude product (2.93 g). H NMR (300 MHz,
CDCl3): δ = 1.22–1.50 (m, 20 H, CH2), 1.71–1.90 (m, 4 H,
OCH2CH2), 2.04 (mc, 4 H, CH2CH=), 3.97 (t, 3J = 6.6 Hz, 2 H,
OCH2), 4.02 (t, 3J = 6.6 Hz, 2 H, OCH2), 4.93 (ddt, 3Jd = 10.2, 2Jd
4
3
2
= 2.0, Jt = 1.2 Hz, 2 H, CH=CHHcis), 4.99 (ddt, Jd = 17.1, Jd
4
3
3
= 2.1, Jt = 1.6 Hz, 2 H, CH=CHHtrans), 5.81 (ddt, Jd = 17.1, Jd
3
4
= 10.3, Jt = 6.7 Hz, 2 H, =CH), 5.90 [s, 2 H, B(OH)2], 6.43 (d, J
= 2.1 Hz, 1 H, 3-CArH), 6.53 (dd, J = 8.3, 4J = 2.1 Hz, 1 H, 5-
3
CArH), 7.74 (d, 3J = 8.3 Hz, 1 H, 6-CArH) ppm. IR (KBr): ν =
˜
3414 (OH), 2926 (aliph. CH), 1605, 1432 (arom. C=C), 1260, 1178,
1019 (COC) cm–1.
3J = 6.4 Hz, 4 H, OCH2), 4.96 (ddt, 3Jd ≈ 10.2, 2Jd = 2.0, 4Jt =
1-Bromo-4-(hex-5-enyloxy)benzene (19a): 4-Bromophenol (18,
2
1.2 Hz, 2 H, =CHHcis), 5.03 (ddt, 3Jd ≈ 17, 4Jd = 2.0, Jt = 1.6 Hz, 2.00 g, 11.6 mmol) was dissolved in dry tetrahydrofuran (60 mL).
3
3
3
2 H, =CHHtrans), 5.83 (ddt, Jd = 17.1, Jd = 10.2, Jt = 6.6 Hz, 2
After addition of hex-5-en-1-ol (15e, 2.07 mL, 17.4 mmol) and tri-
phenylphosphane (3.05 g, 11.6 mmol), the solution was cooled to
H, CH=), 6.44 (d, 4J = 2.1 Hz, 1 H, 3-CArH), 6.46 (brs, 2 H, OH),
6.51 (dd, J = 8.3, J = 2.1 Hz, 2 H, 5-CArH), 7.55 (t, J = 8.1 Hz, 0 °C under nitrogen, diisopropyl azodicarboxylate (DIAD,
3
4
3
6-CArH) ppm. IR (neat): ν = 3384 (OH), 2926 (aliph. CH), 1605,
3.41 mL, 17.4 mmol) was added dropwise, and the solution was
stirred at room temp. for 18 h. The reaction mixture was hydrolysed
˜
1434 (arom. C=C), 1261, 1098 (COC) cm–1. MS (ESI, CH2Cl2/
MeOH): m/z = 369 (100) [M as dimethyl borate + Na]+. An attempt with water (36 mL) and sodium hydroxide solution (2 , 8.5 mL)
to purify phenylboronic acid 17a by column chromatography (silica
gel, cyclohexane/ethyl acetate, 6:1, Rf = 0.57) resulted only in a
colourless liquid [1,3-bis(hex-5-enyloxy)benzene]. 1H NMR
before separation of the layers. The water layer was extracted with
diethyl ether (3ϫ15 mL). The combined organic layer was washed
with brine (15 mL) and dried with magnesium sulfate. The solvent
was evaporated in vacuo, after which the residue was dissolved in
(300 MHz, CDCl3):
δ = = 7.2 Hz, 4 H,
1.56 (quin, 3J
3
CH2CH2CH=), 1.78 (quin, J ≈ 7 Hz, 4 H, CH2CH2O), 2.12 (dtt, dichloromethane (15 mL), and cyclohexane (ca. 300 mL) was
4
3
3Jd,t ≈ 7, Jt = 1.3 Hz, 4 H, CH2CH=), 3.94 (t, J = 6.6 Hz, 4 H,
added to precipitate the phosphane oxide. The precipitate was fil-
tered off and the solvent was evaporated in vacuo. The liquid crude
OCH2), 4.97 (ddt, 3Jd = 10.2, 2Jd = 2.0, 4Jt = 1.3 Hz, 2 H,
=CHHcis), 5.03 (ddt, 3Jd = 17.2, 2Jd = 2.0, 4Jt = 1.6 Hz, 2 H, product was purified by column chromatography (silica gel, cyclo-
=CHHtrans), 5.83 (ddt, 3Jd = 17.1, 3Jd = 10.2, 3Jt = 6.6 Hz, 2 H,
hexane/ethyl acetate, 6:1, Rf = 0.73) to yield a colourless liquid
4
3
4
1
=CH), 6.46 (d, J = 2.2 Hz, 1 H, 2-CArH), 6.47 (dd, J = 8.1, J =
(2.81 g, 11.0 mmol, 95%). H NMR (300 MHz, CDCl3): δ = 1.50–
Eur. J. Org. Chem. 2009, 2328–2341
© 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
2335

F. Eggers, U. Lüning
1.61 (m, 2 H, OCH2CH2CH2), 1.78 (mc, 2 H, OCH2CH2), 2.13 (mc, OCH2(CH2)3CH2(CH2)2], 33.8 (t, CH2CH=), 68.3 (t, OCH2), 112.6
FULL PAPER
3
3
2 H, =CHCH2), 3.91 (t, J = 6.5 Hz, 2 H, OCH2), 4.97 (ddt, Jd =
(s, 1-CAr), 114.2 (t, =CH2), 116.3 (d, 3,5-CAr), 132.2 (d, 2,6-CAr),
2
4
3
10.2, Jd = 2.1, Jt = 1.2 Hz, 1 H, CH=CHHcis), 5.03 (ddt, Jd
=
139.2 (d, CH=CH2), 158.3 (s, 4-CAr) ppm. IR (neat): ν = 3074
˜
2
4
3
17.1, Jd = 2.0, Jt = 1.6 Hz, 1 H, CH=CHHtrans), 5.82 (ddt, Jd =
(arom. CH), 2926 (aliph. CH), 1590, 1489 (arom. C=C), 1244 (C–
17.0, 3Jd = 10.3, Jt = 6.7 Hz, 1 H, CH=CH2), 6.76 (mc with d, 3Jd O–C), 821 (1,4-disubst. benzene) cm–1. MS (EI, 70 eV): m/z (%) =
3
3
= 9.1 Hz, 2 H, 3,5-CArH), 7.35 (mc with d, Jd = 9.1 Hz, 2 H, 2,6-
312, 310 (33, 43) [M]+, 174, 172 (90, 100) [C6H5BrO]+. MS (CI,
isobutane): m/z (%) = 313, 311 (36, 51) [M + H]+, 312, 310 (22, 26)
[M]+, 285, 283 (31, 29) [C14H20BrO]+, 174, 172 (14, 12)
[C6H5BrO]+, 139 (16) [C10H19]+, 111 (100) [C8H15]+. HR-MS (EI,
70 eV): calcd. for C16H2379BrO: 310.0932; found 310.0933 (∆ =
CArH) ppm. 13C NMR (75 MHz, CDCl3):
δ = 25.3 (t,
OCH2CH2CH2), 28.6 (t, OCH2CH2), 33.4 (t, CH2CH=), 68.0 (t,
OCH2), 112.6 (s, 1-CAr), 114.8 (t, =CH2), 116.2 (d, 3,5-CAr), 132.2
(d, 2,6-CAr), 138.4 (d, CH=CH2), 158.2 (s, 4-CAr) ppm. IR (neat):
ν = 2933 (aliph. CH), 1594, 1489 (arom. C=C), 1243 (Ar–O– 0.2 ppm), calcd. for C1513CH2379BrO: 311.0966; found 311.0967 (∆
˜
C) cm–1. MS (EI, 70 eV): m/z (%) = 256, 254 (18, 19) [M]+, 174,
172 (88, 100) [C6H5BrO]+. MS (CI, isobutane): m/z = 257, 255 (94,
= 0.3 ppm), calcd. for C16H2381BrO: 312.0912; found 312.0912 (∆
= 0.1 ppm), calcd. for C1513CH2381BrO: 313.0945; found 313.0946
100) [M + H]+, 256, 254 (35, 30) [M]+, 174, 172 (30, 34) (∆ = 0.2 ppm). C16H23BrO (310.09): calcd. C 61.74, H 7.45; found
[C6H5BrO]+. C12H15BrO (254.03): calcd. C 56.49, H 5.93; found C
56.40, H 5.99.
C 61.79, H 7.66.
4-(Hex-5-enyloxy)phenylboronic Acid (20a): 1-Bromo-4-(hex-5-en-
yloxy)benzene (19a, 1.00 g, 3.94 mmol) was dissolved in dry tetra-
hydrofuran (25 mL) and cooled to –78 °C under nitrogen. After
addition of n-butyllithium (1.73 mL, 4.35 mmol, 2.5  in hexanes),
the solution was stirred at –78 °C for 1 h before addition of tri-
methyl borate (1.29 mL, 13.1 mmol) and was then stirred for an-
other 2 h while warming to room temp. Water (20 mL) was then
added, and the layers were separated. The water layer was extracted
with diethyl ether (3ϫ15 mL). The combined organic layer was
washed with brine (20 mL) and dried with magnesium sulfate.
Evaporation of the solvent in vacuo yielded a crystalline crude
product. This crude product (300 mg) was recrystallised to yield
1-Bromo-4-(oct-7-enyloxy)benzene (19b): This compound was syn-
thesised by the procedure used for 1-bromo-4-(hex-5-enyloxy)ben-
zene (19a), with 4-bromophenol (18, 1.00 g, 5.80 mmol), oct-7-en-
1-ol (15f, 1.11 g, 8.70 mmol), triphenylphosphane (1.53 g,
5.80 mmol), and diisopropyl azodicarboxylate (DIAD, 1.71 mL,
8.70 mmol) in dry tetrahydrofuran (30 mL). The crude product was
purified by column chromatography (silica gel, cyclohexane/ethyl
acetate, 6:1, Rf ≈ 0.70) to yield a colourless liquid (1.43 g,
1
5.05 mmol, 87%). H NMR (300 MHz, CDCl3): δ = 1.32–1.51 [m,
6 H, OCH2CH2(CH2)3], 1.77 (mc, 2 H, OCH2CH2), 2.06 (mc, 2 H,
=CHCH2), 3.91 (t, 3J = 6.5 Hz, 2 H, OCH2), 4.94 (ddt, 3Jd = 10.2,
4
3
2Jd = 2.2, Jt = 1.2 Hz, 1 H, CH=CHHcis), 4.99 (ddt, Jd = 17.1, colourless crystals (250 mg). The product crystallises as a mixture
4
3
2Jd = 2.1, Jt = 1.6 Hz, 1 H, CH=CHHtrans), 5.81 (ddt, Jd = 17.1,
of monomer and trimer of the boronic acid, as was shown by its
mass spectra and NMR spectra. Crude product: 950 mg, m.p. 93–
97 °C (cyclohexane/dichloromethane), monomer/trimer. 1H NMR
(600 MHz, [D6]DMSO): δ = 1.50 (mc, 2 H, OCH2CH2CH2), 1.72
3Jd = 10.2, 3Jt = 6.7 Hz, 1 H, CH=CH2), 6.77 (mc with d, 3Jd
=
9.0 Hz, 2 H, 3,5-CH), 7.35 (mc with d, 3Jd = 9.1 Hz, 2 H, 2,6-
CH) ppm. 13C NMR (75 MHz, CDCl3): δ = 25.9, 28.8, 29.0, 29.1,
29.2, 29.5 (t, CH2), 33.7 (t, CH2CH=), 68.3 (t, OCH2), 112.6 (s, 1- (mc, 2 H, OCH2CH2), 2.09 (mc, 2 H, CH2CH=), 3.98 (t, 3J =
3
2
4
CAr), 114.3 (t, =CH2), 116.4 (d, 3,5-CAr), 132.2 (d, 2,6-CAr), 139.0
6.5 Hz, 2 H, OCH2), 4.97 (ddt, Jd = 10.2, Jd = 2.2, Jt = 1.2 Hz,
3
2
4
(d, CH=CH2), 158.3 (s, 4-CAr) ppm. IR (neat): ν = 2926 (aliph.
1 H, CH=CHHcis), 5.03 (ddt, Jd = 17.2, Jd = 2.1, Jt = 1.6 Hz, 1
˜
3
3
3
CH), 1590, 1489 (arom. C=C), 1244 (C–O–C), 821 (1,4-disubst.
benzene) cm–1. MS (EI, 70 eV): m/z = 284, 282 (100, 88) [M]+, 174,
172 (62, 52) [C6H5BrO]+. MS (CI, isobutane): m/z (%) = 285, 283
H, CH=CHHtrans), 5.82 (ddt, Jd = 17.1, Jd = 10.3, Jt = 6.7 Hz,
1 H, CH=CH2), 6.87 (mc with d, 3J = 8.7 Hz, 2 H, 3,5-CArH), 7.72
(mc with d, 3J = 8.7 Hz, 2 H, 2,6-CArH) ppm. 13C NMR (150 MHz,
(60, 58) [M + H]+, 174, 172 (14, 14) [C6H5BrO]+, 111 (100) [D6]DMSO): δ = 24.7 (t, OCH2CH2CH2), 28.1 (t, OCH2CH2), 32.8
[C8H15]+. HR-MS (EI, 70 eV): calcd. for C14H1979BrO: 282.0619;
found 282.0619 (∆ = 0 ppm), calcd. for C1313CH1979BrO: 283.0653;
found 283.0653 (∆ = 0.2 ppm), calcd. for C14H1981BrO: 284.0599;
(t, CH2CH=), 66.9 (t, OCH2), 113.4 (d, 3,5-CAr), 114.9 (t,
CH=CH2), 135.8 (d, 2,6-CAr), 138.5 (d, CH=CH2), 160.3 (s, 4-
CAr) ppm. IR (KBr): ν = 3220 (OH), 2943 (aliph. CH), 1602, 1415
˜
found 284.0600 (∆
=
0.4 ppm), calcd. for C1313CH1981BrO:
(arom. C=C), 1351 (OH-deform.), 1245 (Ar–O–C) cm–1. Because
of relaxation effects with the 11B isotope, the signal of 1-CAr is
weak and could not be detected. MS (EI, 70 eV): m/z (%) = 606
285.0632; found 285.0631 (∆ = 0.5 ppm). C14H19BrO (282.06):
calcd. C 59.37, H 7.20. C14H19BrO·0.3C6H12 (282.06 + 25.23):
calcd. C 61.52, H 7.39; found C 61.18, H 7.55.
(77) [M(trimer)]+, 524 (3) [M(trimer)
–
C6H10]+, 523 (3)
[M(trimer) – C6H11]+, 360 (100) [M(trimer) – 3C6H10]+, 221 (3) [M
+ H]+. C36H45B3O6 (trimer, 606.35): calcd. C 71.33, H 7.48; found
C 71.63, H 7.76.
1-Bromo-4-(dec-9-enyloxy)benzene (19c): This compound was syn-
thesised by the procedure described for 1-bromo-4-(hex-5-enyloxy)-
benzene (19a), with 4-bromophenol (18, 3.00 g, 17.4 mmol), dec-9-
en-1-ol (15d, 4.83 mL, 4.08 g, 26.1 mmol), triphenylphosphane
(4.59 g, 17.4 mmol) and diisopropyl azodicarboxylate (DIAD,
5.13 mL, 26.1 mmol) in dry tetrahydrofuran (60 mL). The crude
product was purified by column chromatography (silica gel, cyclo-
hexane/ethyl acetate, 6:1, Rf ≈ 0.80) to yield a colourless liquid
4-(Oct-7-enyloxy)phenylboronic Acid (20b): This compound was
synthesised by the procedure used for the synthesis of 4-(hex-5-
enyloxy)phenylboronic acid (20a), from 1-bromo-4-(oct-7-enyloxy)-
benzene (19b, 1.00 g, 3.53 mmol), n-butyllithium (1.55 mL,
3.89 mmol, 2.5  in hexanes) and trimethyl borate (1.15 mL,
(4.27 g, 13.7 mmol, 79%); m.p. Ͻ18 °C. 1H NMR (500 MHz, 11.7 mmol) in dry tetrahydrofuran (20 mL), to yield crude colour-
CDCl3): δ = 1.26–1.46 [m, 10 H, OCH2CH2(CH2)5], 1.76 (mc, 2 H, less crystals (820 mg). This crude product (200 mg) was recrystal-
OCH2CH2), 2.04 (mc, 2 H, =CHCH2), 3.90 (t, 3J = 6.6 Hz, 2 H,
lised (cyclohexane) to yield phenylboronic acid 20b (180 mg); m.p.
76 °C, 148 °C (monomer/trimer). The product crystallises as a mix-
OCH2), 4.97 (ddt, 3Jd = 10.2, 2Jd = 2.1, 4Jt = 1.2 Hz, 1 H,
3
2
4
CH=CHHcis), 5.03 (ddt, Jd = 17.1, Jd = 2.1, Jt = 1.6 Hz, 1 H, ture of monomer and trimer of the boronic acid, which was shown
CH=CHHtrans), 5.81 (ddt, 3Jd = 17.0, 3Jd = 10.2, 3Jt = 6.7 Hz, 1 by its mass spectra and NMR spectra. 1H NMR (300 MHz,
3
H, CH=CH2), 6.76 (mc with d, Jd = 9.0 Hz, 2 H, 3,5-CArH), 7.35 CDCl3): δ = 1.25–1.55 (m, 6 H, OCH2CH2CH2), 1.82 (mc, 2 H,
(mc with d, 3Jd = 9.0 Hz, 2 H, 2,6-CArH) ppm. 13C NMR (75 MHz, OCH2CH2), 2.07 (mc, 2 H, CH2CH=), 4.04 (t, 3J = 6.5 Hz, 2 H,
CDCl3): δ = 26.0 [t, O(CH2)4CH2], 28.9, 29.1, 29.2, 29.3, 29.4 [t,
OCH2), 4.95 (ddt, 3Jd = 10.1, 2Jd = 2.1, 4Jt = 1.2 Hz, 1 H,
2336
www.eurjoc.org
© 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 2009, 2328–2341

Concave 1,10-Phenanthrolines as Ligands for Cyclopropanations
3
2
4
CH=CHHcis), 5.01 (ddt, Jd = 17.1, Jd = 2.1, Jt = 1.6 Hz, 1 H, to ethyl acetate, Rf ≈ 0.10) to yield slightly yellow crystals (185 mg,
CH=CHHtrans), 5.83 (mc with ddt, 3Jd = 17.1, 3Jd = 10.2, 3Jt =
6.7 Hz, 1 H, CH=CH2), 7.00 (mc with d, J = 8.7 Hz, 3,5-CArH),
8.15 (mc with d, J = 8.7 Hz, 2 H, 2,6-CArH) ppm. IR (KBr): ν =
3400 (OH), 2927 (aliph. CH), 1602, 1412 (arom. C=C), 1350, 1246, 4 H, CH2CH=), 2.16 (dtt, Jt = 7.3, Jd = 6.9, Jt = 1.3 Hz, 4 H,
256 µmol, 27%); m.p. 193–195 °C. 1H NMR (600 MHz, CDCl3): δ
= 1.54 [mc, 4 H, O(CH2)2CH2], 1.61 [mc, 4 H, O(CH2)2CH2], 1.83
3
3
3
3
4
(mc, 8 H, OCH2CH2), 2.08 (dtt, Jt = 7.3, Jd = 6.9, Jt = 1.3 Hz,
˜
3
3
4
1171 (C–O–C) cm–1. Not only could the signals of the trimer of the
boronic acid be found, but also signals that probably belong to the
dimer or monomer. The intensities of these signals were small in
comparison to the signals of the trimer. 13C NMR (150 MHz,
CDCl3): δ = 25.9, 28.9, 29.2, 29.4, 29.5 (t, CH2), 29.7 (t,
CH2CH=), 4.04 (t, J = 6.4 Hz, 4 H, OCH2), 4.05 (t, J = 6.5 Hz,
4 H, OCH2), 4.94 (ddt, 3Jd = 10.2, 2Jd = 2.0, 4Jt = 1.3 Hz, 2 H,
=CHHcis), 4.99 (ddt, 3Jd = 10.2, 2Jd = 2.0, 4Jt = 1.3 Hz, 2 H,
=CHHcis), 5.00 (ddt, 3Jd = 17.2, 2Jd = 2.0, 4Jt = 1.6 Hz, 2 H,
=CHHtrans), 5.06 (ddt, 3Jd = 17.1, 2Jd = 2.0, 4Jt = 1.6 Hz, 2 H,
3
3
OCH2CH2), 33.7 (t, CH2CH=), 67.9 (t, OCH2), 114.1 (d, 3,5-CAr), =CHHtrans), 5.78 (ddt, 3Jd = 17.0, 3Jd = 10.3, 3Jt = 6.7 Hz, 2 H,
3
3
3
114.3 (t, CH=CH2), 137.5 (d, 2,6-CAr), 139.1 (d, CH=CH2), 149.4
(s, 1-CAr), 162.8 (s, 4-CAr) ppm. MS (EI, 70 eV): m/z (%) = 690 (91)
[M(trimer)]+, 580 (6) [M(trimer) – C8H14]+, 360 (100) [M(trimer) –
3C8H14]+. C42H57B3O6 (trimer, 690.44): calcd. C 73.07, H 8.32.
C42H57B3O6·C6H12 (trimer, 690.44 + 84.10): calcd. C 74.44, H 9.98;
found C 74.61, H 8.71.
=CH), 5.86 (ddt, Jd = 17.0, Jd = 10.3, Jt = 6.7 Hz, 2 H, =CH),
6.56 (d, 4J = 2.4 Hz, 2 H, 3-CArH), 6.72 (dd, 3J = 8.6, J = 2.3 Hz,
2 H, 5-CArH), 7.72 (s, 2 H, 5,6-CPhenH), 8.16 (d, J = 8.5 Hz, 2 H,
4
3
3
3
3,8-CPhenH), 8.28 (d, J = 8.4 Hz, 2 H, 4,7-CPhenH), 8.38 (d, J =
8.6 Hz, 2 H, 6-CArH) ppm. Assignment of the signals to the ortho-
and para-side chains was not reliably possible from these data. Cal-
culations from an increment system for NMR spectra of aromatic
compounds[27] predict that the signals of a substituent in a para
position should be shifted to higher fields than signals of the same
substituent in an ortho position, and the signals are assigned on
these grounds. 13C NMR (150 MHz, CDCl3): δ = 25.3, 25.4 (2ϫt,
OCH2CH2), 28.6, 28.7 (2ϫt, OCH2CH2), 33.2, 33.5 (2ϫt,
CH2CH=), 67.8, 68.4 (2ϫt, OCH2), 100.2 (d, 3-CAr), 106.0 (d, 5-
4-(Dec-9-enyloxy)phenylboronic Acid (20c): This compound was
synthesised by the procedure used for the synthesis of 4-(hex-5-
enyloxy)phenylboronic acid (20a), from 1-bromo-4-(dec-9-enyl-
oxy)benzene (19c, 1.21 g, 3.89 mmol), n-butyllithium (1.71 mL,
4.29 mmol, 2.5  in hexanes), and trimethyl borate (1.27 mL,
12.9 mmol) in dry tetrahydrofuran (22 mL), to yield crude colour-
less crystals (993 mg). This crude product (250 mg) was recrystal-
lised (cyclohexane) to yield the boronic acid (195 mg); m.p. 58–
60 °C, 130 °C (monomer/trimer). The product crystallises as a mix-
ture of monomer and trimer of the boronic acid, which was shown
by its mass spectra and NMR spectra. 1H NMR (300 MHz,
CDCl3): δ = 1.26–1.53 (m, 15 H, CH2), 1.81 (mc, 3 H, OCH2CH2),
CAr), 114.8 (2ϫt, =CH2), 122.7 (s, 1-CAr), 124.6 (d, 3,8-CPhen),
125.5 (d, 5,6-CPhen), 127.0 (s, 4a,6a-CPhen), 133.2 (d, 6-CAr), 135.0
(d, 4,7-CPhen), 138.6 (2ϫd, CH=), 146.0 (s, 10a,10b-CPhen), 156.0
(s, 2,9-CPhen), 158.2 (s, 4-CAr), 161.1 (s, 2-CAr) ppm. The assign-
ment of the signals is based on the prediction that signals of a para-
substituent are shifted to higher fields than the signals of an ortho-
substituent. This assumption is based on calculations made with
an increment system for NMR spectra of substituted aromatic
3
2.05 (mc, 3 H, CH2CH=), 4.04 (t, J = 6.5 Hz, 3 H, OCH2), 4.96
3
2
4
(ddt, Jd = 10.2, Jd = 2.1, Jt = 1.2 Hz, 1.5 H, CH=CHHcis), 5.00
(ddt, 3Jd = 17.1, 2Jd = 2.2, 4Jt = 1.6 Hz, 1.5 H, CH=CHHtrans),
compounds.[27] IR (KBr): ν = 2925 (aliph. CH), 1608, 1456 (arom.
˜
3
3
3
5.82 (ddt, Jd = 17.1, Jd = 10.2, Jt = 6.7 Hz, 1.5 H, CH=CH2),
C=C), 1257, 1090 (COC) cm–1. MS (EI, 70 eV): m/z (%) = 724
(100) [M]+, 696 (30) [C46H52N2O4]+, 669 (22) [C44H49N2O4]+, 655
(62) [C43H47N2O4]+, 641 (29) [C42H45N2O4]+, 625 (19)
[C42H45N2O3]+, 573 (24) [C37H37N2O4]+, 560 (27) [C36H36N2O4]+,
379 (19) [C24H15N2O3]+. MS (ESI, CHCl3/MeOH): m/z (%) = 725
(100) [M + H]+. HR-MS (EI, 70 eV): C48H56N2O4, calcd. 724.4240;
found 724.4240 (∆ = 0 ppm), C4713CH56N2O4, calcd. 725.4273;
found 725.4274 (∆ = 0.1 ppm), C4613C2H56N2O4, calcd. 726.4305;
found 726.4307 (∆ = 0.2 ppm). C48H56N2O4 (724.42): calcd. C
79.52, H 7.79, N 3.86. C48H56N2O4·0.3H2O (724.42 + 5.40): calcd.
C 78.93, H 7.81, N 3.84; found C 78.86, H 7.73, N 3.88.
3
3
6.96 (d, J = 8.6 Hz, 1 H, 3,5-CArHmonomer), 7.00 (mc with d, J =
8.6 Hz, 2 H, 3,5-CArHtrimer), 7.27 (brs, 1 H, OH), 7.75 (d, 3J =
3
8.6 Hz, 1 H, 2,6-CArHmonomer), 8.15 (mc with d, J = 8.7 Hz, 2 H,
2,6-CArHtrimer) ppm. 13C NMR (150 MHz, CDCl3): δ = 26.1, 28.9,
29.1, 29.3, 29.37 (t, CH2), 29.42 (t, OCH2CH2), 33.8 (t, CH2CH=),
67.9 (t, OCH2), 114.1 (t, CH=CH2), 114.2 (d, 3,5-CArmonomer),
116.0 (d, 3,5-CArtrimer), 129.4 (d, 2,6-CArmonomer), 136.6 (d, 2,6-
CArtrimer), 137.5 (d, CH=CH2), 162.3 (s, 4-CAr) ppm. Because of
relaxation effects with the 11B isotope, the signal of 1-CAr is weak
and could not be detected. IR (KBr): ν = 3356 (OH), 2924 (aliph.
˜
CH), 1605, 1351 (arom. C=C), 1248 (C–O–C), 823 (1,4-disubst.
benzene) cm–1. MS (EI, 70 eV): m/z (%) = 774 (29) [M(trimer)]+,
360 (100) [M(trimer) – 3C10H18]+. C16H25BO3 (monomer, 276.19):
calcd. C 69.58, H 9.12; found C 69.81, H 9.08.
2,9-Bis[2,4-bis(dec-9-enyloxy)phenyl]-1,10-phenanthroline
(21b).
Method A: 2,9-Diiodo-1,10-phenanthroline (12, 113 mg, 263 µmol)
was dissolved in 1,2-dimethoxyethane (8 mL) and water (2 mL).
After addition of crude 2,4-bis(dec-9-enyloxy)phenylboronic acid
(17b, 510 mg, max. 1.19 mmol), tetrakis(triphenylphosphane)palla-
dium(0) (32 mg, 26 µmol) and barium hydroxide octahydrate
(384 mg, 1.19 mmol), the mixture was stirred at 80 °C under nitro-
gen for 40 h. To complete the reaction, the mixture was allowed to
cool to room temp., additional crude 2,4-bis(dec-9-enyloxy)phen-
ylboronic acid (17b, 210 mg, max. 490 µmol) and tetrakis(triphen-
ylphosphane)palladium(0) (5.0 mg, 4.1 µmol) were then added, and
stirring was continued at 80 °C under nitrogen for another 40 h.
2,9-Bis[2,4-bis(hex-5-enyloxy)phenyl]-1,10-phenanthroline (21a): 2,9-
Diiodo-1,10-phenanthroline (12, 300 mg, 694 µmol) was dissolved
in 1,2-dimethoxyethane (21 mL) and water (5 mL). After addition
of crude 2,4-bis(hex-5-enyloxy)phenylboronic acid (17a, 665 mg,
max.
2.09 mmol),
tetrakis(triphenylphosphane)palladium(0)
(85.0 mg, 73.8 µmol) and barium hydroxide octahydrate (1.01 g,
3.14 mmol), the reaction mixture was heated to 60 °C under nitro-
gen for 16 h. After the system had cooled to room temp., water
and dichloromethane (20 mL each) were added to the suspension
and the layers were separated. The water layer was extracted with After addition of dichloromethane and water (10 mL each) and
dichloromethane (3ϫ20 mL), and the combined organic layer was
washed once with brine (20 mL) and dried with magnesium sulfate.
The solvent was evaporated and the residue was filtered through
basic aluminium oxide (dichloromethane). Evaporation of the sol-
vent was followed by purification of the crude product by column
chromatography (Chromatotron, 2 mm, silica gel, dichloromethane
separation of the layers, the water layer was extracted with dichlo-
romethane (3ϫ10 mL). The combined organic layer was washed
with brine (10 mL) and dried with magnesium sulfate. After evapo-
ration of the solvent in vacuo, the crude product was purified by
chromatography (Chromatotron, 2 mm, silica gel, dichlorometh-
ane/ethyl acetate, 4:1, Rf ≈ 0.10) to yield a colourless oil (25 mg,
Eur. J. Org. Chem. 2009, 2328–2341
© 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
2337

F. Eggers, U. Lüning
FULL PAPER
26 µmol, 10%). MS (ESI, CHCl3/MeOH, crude product): m/z (%)
OCH2), 5.00 (ddt, 3Jd = 10.2, 2Jd = 2.0, 4Jt = 1.2 Hz, 2 H,
3
2
4
= 949.7 (100) [M + H]+.
CH=CHHcis), 5.06 (ddt, Jd = 17.1, Jd = 2.0, Jt = 1.6 Hz, 2 H,
CH=CHHtrans), 5.86 (ddt, 3Jd = 17.1, 3Jd = 10.2, 3Jt = 6.7 Hz, 2
Method B: 2-[2,4-Bis(dec-9-enyloxy)phenyl]-9-chloro-1,10-phenan-
throline (23, 90.0 mg, 151 µmol) was dissolved in 1,2-dimethoxy-
ethane (6 mL) and water (1.5 mL). After addition of tetrakis(tri-
phenylphosphane)palladium(0) (18 mg, 15 µmol), crude 2,4-
bis(dec-9-enyloxy)phenylboronic acid (17b, 360 mg, max.
838 µmol) and barium hydroxide octahydrate (100 mg, 341 µmol),
the mixture was stirred at 80 °C under nitrogen for 18 h. Cooling
down to room temp. was followed by addition of dichloromethane
and water (10 mL each) and separation of the layers. The water
layer was extracted with dichloromethane (3ϫ10 mL). The com-
bined organic layer was washed with brine (10 mL) and dried with
magnesium sulfate. After evaporation of the solvent in vacuo, the
crude product was purified by chromatography (Chromatotron,
2 mm, silica gel, dichloromethane/ethyl acetate, 4:1, Rf ≈ 0.10) to
3
H, CH=CH2), 7.09 (mc with d, J = 8.9 Hz, 4 H, 3,5-CArH), 7.71
3
(s, 2 H, 5,6-CPhenH), 8.06 (d, J = 8.4 Hz, 2 H, 3,8-CPhenH), 8.23
(d, 3J = 8.4 Hz, 2 H, 4,7-CPhenH), 8.42 (mc with d, 3J = 8.9 Hz,
4 H, 2,6-CArH) ppm. 13C NMR (150 MHz, CDCl3): δ = 25.4 (t,
OCH2CH2CH2), 28.8 (t, OCH2CH2), 33.5 (t, CH2CH=), 67.9 (t,
OCH2), 114.8 (t, =CH2), 114.8 (d, 3,5-CAr), 119.3 (d, 3,8-CPhen),
125.6 (d, 5,6-CPhen), 127.5 (s, 4a,6a-CPhen), 129.0 (d, 2,6-CAr), 132.1
(s, 1-CAr), 136.7 (d, 4,7-CPhen), 138.6 (d, CH=CH2), 146.1 (s,
10a,10b-CPhen), 156.4 (s, 2,9-CPhen), 160.5 (s, 4-CAr) ppm. IR
(KBr): ν = 2939 (aliph. CH), 1601, 1492 (arom. C=C), 1246 (Ar–
˜
O–C) cm–1. MS (EI, 70 eV): m/z (%) = 528 (100) [M]+, 446 (7) [M –
C6H10]+, 364 (19) [M – 2C6H10]+. HR-MS (ESI, CHCl3/MeOH):
C36H36N2O2 (528.28), calcd. for C36H36N2O2 + H+: 529.2850;
found 529.2803 (∆ = 8.9 ppm), calcd. for C3513CH36N2O2 + H+:
530.2882; found 530.2848 (∆ = 6.4 ppm), calcd. for 2C36H36N2O2
+ Na+: 1079.5446; found 1079.5354 (∆ = 8.5 ppm), calcd. for
C3513CH36N2O2·C36H36N2O2 + Na+: 1080.5478; found 1080.5447
(∆ = 2.9 ppm), calcd. for 2C3513CH36N2O2: 1081.5511; found
1
yield a colourless oil (60 mg, 63 µmol, 42%). H NMR (500 MHz,
CDCl3): δ = 1.21–1.49 (m, 40 H, CH2), 1.49 (mc, 4 H, CH2), 1.80
(mc, 8 H, OCH2CH2), 2.00 (mc, 4 H, CH2CH=), 2.06 (mc, 4 H,
3
3
CH2CH=), 4.03 (t, J = 6.3 Hz, 4 H, OCH2), 4.04 (t, J = 6.5 Hz,
4 H, OCH2), 4.91 (ddt, 3Jd = 10.2, 2Jd = 2.2, 4Jt = 1.2 Hz, 2 H,
1081.5528 (∆
C36H36N2O2: 528.2777; found 528.2778 (∆ = 0.1 ppm), calcd. for
C3513CH36N2O2: 529.2810; found 529.2812 (∆
0.2 ppm).
C36H36N2O2 (528.28): calcd. 81.79, 6.86, 5.30.
= 1.6 ppm). HR-MS (EI, 70 eV): calcd. for
CH=CHHcis), 4.94 (ddt, Jd ≈ 10.2, Jd = 2.2, 4Jt = 1.2 Hz, 2 H,
3
2
3
2
4
CH=CHHcis), 4.97 (ddt, Jd = 17.2, Jd = 2.2, Jt = 1.6 Hz, 2 H,
CH=CHHtrans), 5.01 (ddt, Jd = 17.1, Jd = 2.2, Jt = 1.6 Hz, 2 H,
=
3
2
4
C
H
N
3
3
3
CH=CHHtrans), 5.80 (2ϫddt, Jd = 17.1, Jd = 10.2, Jt = 6.7 Hz,
C36H36N2O2·0.1H2O (528.28 + 1.80): calcd. C 81.51, H 6.88, N
5.28; found C 81.36, H 6.98, N 5.14.
4 H, CH=CH2), 6.57 (d, J = 2.3 Hz, 2 H, 3-CArH), 6.71 (dd, 3J =
4
4
8.6, J = 2.3 Hz, 2 H, 5-CArH), 7.73 (s, 2 H, 5,6-CPhenH), 8.16 (d,
3J = 8.4 Hz, 2 H, 4,7-CPhenH), 8.29 (d, 3J = 8.4 Hz, 2 H, 3,8- 2,9-Bis[4-(oct-7-enyloxy)phenyl]-1,10-phenanthroline (22b): This
CPhenH), 8.38 (d, 3J = 8.6 Hz, 2 H, 6-CArH) ppm. 13C NMR
(150 MHz, CDCl3): δ = 26.1 (d, CH2), 26.2 (d, CH2), 28.9 (2ϫd,
compound was synthesised as described above by the procedure for
the synthesis of 2,9-bis[4-(hex-5-enyloxy)phenyl]-1,10-phenan-
CH2), 29.0 (d, CH2), 29.1 (d, CH2), 29.2 (d, CH2), 29.3 (d, CH2), throline (22a), from 2,9-diiodo-1,10-phenanthroline (12, 60.0 mg,
29.4 (2ϫd, CH2), 29.5 (d, CH2), 33.8 (2ϫd, CH2CH=), 68.2 (d, 246 µmol), crude 4-(oct-7-enyloxy)phenylboronic acid (20b,
OCH2), 68.8 (d, OCH2), 100.4 (d, 3-CAr), 106.2 (d, 5-CAr), 114.2 183 mg, max. 739 µmol), barium hydroxide octahydrate (359 mg,
(2ϫt, =CH2), 123.7 (s, 4-CAr), 124.5 (d, 3,8-CPhen), 125.5 (d, 6- 1.11 mmol), and tetrakis(triphenylphosphane)palladium(0) (30 mg,
CAr), 127.0 (d, 5,6-CPhen), 130.8 (s, 4a,6a-CPhen), 133.4 (s, 10a,10b-
25 µmol) in 1,2-dimethoxyethane (8 mL) and water (2 mL). The
CPhen), 134.9 (d, 4,7-CPhen), 139.2 (2ϫd, CH=CH2), 156.1 (s, 2,9- crude product was purified by column chromatography (silica gel,
C
Phen), 158.4 (s, 2-CAr), 161.2 (s, 1-CAr) ppm. IR (KBr): ν = 3075
cyclohexane/ethyl acetate, 4:1, Rf = 0.75) to yield colourless crystals
(66 mg, 113 µmol, 46%). H NMR (600 MHz, CDCl3): δ = 1.39–
˜
1
(arom. CH), 2926 (aliph. CH), 1605, 1432 (arom. C=C), 1295, 1180
(COC) cm–1. MS (ESI, CHCl3/MeOH): m/z (%) = 949.7 (100) [M
+ H]+. MS (EI, 70 eV): m/z (%) = 948.7 (29) [M]+, 823.7 (69) [M –
1.49 (m, 8 H, CH2), 1.51 (mc, 4 H, OCH2CH2CH2), 1.83 (mc, 4 H,
OCH2CH2), 2.05 (mc, 4 H, CH2CH=), 4.06 (t, 3J = 6.6 Hz, 4 H,
C9H17]+, 810 (21) [M – C10H19]+. HR-MS (EI, 70 eV): C64H88N2O4 OCH2), 4.95 (ddt, 3Jd = 10.2, 2Jd = 2.1, 4Jt = 1.1 Hz, 2 H,
(948.67), calcd. for C64H88N2O4 + H+: 949.6817; found 949.6851 CH=CHHcis), 5.02 (ddt, Jd = 17.0, Jd = 2.1, Jt = 1.6 Hz, 2 H,
3
2
4
(∆ = 3.6 ppm), calcd. for C6313CH88N2O4 + H+: 950.6850; found
950.6866 (∆ = 1.7 ppm). C64H88N2O4 (948.67): calcd. C 76.16, H
7.91, N 4.67. C64H88N2O4·0.5C6H12 (948.67 + 42.05): calcd. C
76.78, H 8.33, N 4.37; found C 76.90, H 8.34, N 4.12.
CH=CHHtrans), 5.82 (ddt, 3Jd = 17.1, 3Jd = 10.3, 3Jt = 6.7 Hz, 2
3
H, CH=CH2), 7.08 (mc with d, J = 8.8 Hz, 4 H, 3,5-CArH), 7.70
3
(s, 2 H, 5,6-CPhenH), 8.04 (d, J = 8.4 Hz, 2 H, 3,8-CPhenH), 8.22
3
3
(d, J = 8.4 Hz, 2 H, 4,7-CPhenH), 8.39 (mc with d, J = 8.8 Hz, 4
H, 2,6-CArH) ppm. 13C NMR (150 MHz, CDCl3): δ = 25.9, 28.9,
29.3, 29.4 [t, OCH2(CH2)4], 33.7 (t, CH2CH=), 68.1 (t, OCH2),
114.8 (t, =CH2), 115.6 (d, 3,5-CAr), 119.5 (d, 3,8-CPhen), 125.6 (d,
5,6-CPhen), 127.5 (s, 4a,6a-CPhen), 129.1 (d, 2,6-CAr), 132.0 (s, 1-
CAr), 136.8 (d, 4,7-CPhen), 139.0 (d, CH=CH2), 146.0 (s, 10a,10b-
2,9-Bis[4-(hex-5-enyloxy)phenyl]-1,10-phenanthroline (22a): 2,9-Di-
iodo-1,10-phenanthroline (12) was dissolved in 1,2-dimethoxy-
ethane (17 mL) and water (4.3 mL) before addition of 4-(hex-5-
enyloxy)phenylboronic acid (20a, 433 mg, max. 1.97 mmol of the
monomer), barium hydroxide octahydrate (958 mg, 2.97 mmol) and
tetrakis(triphenylphosphane)palladium(0) (80 mg, 66 µmol). The
mixture was stirred at 80 °C under nitrogen for 72 h and allowed
to cool to room temp., and water and dichloromethane (20 mL
each) were added. The layers were separated and the water layer
was extracted with dichloromethane (3 ϫ 20 mL). The combined
organic layer was washed with brine (20 mL) and dried with mag-
nesium sulfate. Evaporation of the solvent in vacuo was followed
by purification of the crude product by column chromatography
(silica gel, cyclohexane/ethyl acetate, 4:1, Rf = 0.26) to yield colour-
CPhen), 156.6 (s, 2,9-CPhen), 160.5 (s, 4-CAr) ppm. IR (KBr): ν =
˜
2930 (aliph. CH), 1598, 1459 (arom. C=C), 1249, 1176 (C–O–
C) cm–1. MS (EI, 70 eV): m/z (%) = 584 (100) [M]+, 474 (16) [M –
C8H14]+, 364 (29) [M – 2C8H14]+. MS (ESI, CHCl3/MeOH): m/z
(%) = 585 (100) [M + H]+. HR-MS (EI, 70 eV): calcd. for
C40H44N2O2: 584.3403; found 584.3403 (∆ ≈ 0.1 ppm), calcd. for
C3913CH44N2O2: 585.3436; found 585.3437 (∆ = 0.1 ppm).
2,9-Bis[4-(dec-9-enyloxy)phenyl]-1,10-phenanthroline (22c): This
compound was synthesised as described above by the procedure
less crystals (103 mg, 195 µmol, 30%). 1H NMR (600 MHz, used for 2,9-bis[4-(hex-5-enyloxy)phenyl]-1,10-phenanthroline
CDCl3): δ = 1.62 (mc, 4 H, OCH2CH2CH2), 1.86 (mc, 4 H, (20a), from 2,9-diiodo-1,10-phenanthroline (12, 50.0 mg,
OCH2CH2), 2.17 (mc, 4 H, CH2CH=), 4.08 (t, 3J = 6.5 Hz, 4 H,
116 µmol), crude 4-(dec-9-enyloxy)phenylboronic acid (20c,
2338
www.eurjoc.org
© 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 2009, 2328–2341

Concave 1,10-Phenanthrolines as Ligands for Cyclopropanations
170 mg, max. 616 µmol of the monomer), barium hydroxide octa-
hydrate (299 mg, 928 µmol), and tetrakis(triphenylphosphane)pal-
ladium(0) (25 mg, 21 µmol) in 1,2-dimethoxyethane (6 mL) and
water (1.5 mL). The crude product was purified by column
(d, 6-CPhen*), 127.4 (2ϫs, 10a,10b-CPhen), 133.5 (d, 4-CPhen), 134.9
(d, 7-CPhen), 138.6 (d, 3-CPhen), 139.1 (d, CH=CH2), 139.2 (d,
CH=CH2), 144.9 (s, 4a-CPhen#), 146.4 (s, 6a-CPhen#), 151.2 (s, 2-
CPhen), 157.1 (s, 9-CPhen), 158.3 (s, 2-CAr), 161.5 (s, 1-CAr) ppm.
chromatography (silica gel, cyclohexane/ethyl acetate, 4:1, Rf
=
The assignments marked with #, * may be reversed. IR (KBr): ν
˜
1
0.53) to yield yellow crystals (105 mg, 164 µmol, 80%). H NMR
(600 MHz, CDCl3): δ = 1.30–1.47 (m, 8 H, CH2), 1.48–1.55 (m, 8
= 2925 (aliph. CH), 1608, 1580, 1476 (arom. C=C), 1279, 1182
(COC) cm–1. MS (EI, 70 eV): m/z = 600, 598 (7, 24) [M]+, 475, 473
H, CH2), 1.84 (mc, 4 H, OCH2CH2), 2.06 (mc, 4 H, =CHCH2), (34, 100) [M – C9H17]+, 308, 306 (12, 40) [M + H – C10H18
–
3
3
2
4.07 (t, J = 6.6 Hz, 4 H, OCH2), 4.94 (ddt, Jd = 10.2, Jd = 2.2,
C10H19O]+. MS (ESI, CHCl3/MeOH): m/z (%) = 601, 599 (45, 100)
4Jt = 1.2 Hz, 2 H, CH=CHHcis), 5.01 (ddt, Jd = 17.1, Jd = 2.1, [M + H]+. HR-MS (EI, 70 eV): calcd. for C38H4735ClN2O2:
3
2
4Jt = 1.6 Hz, 2 H, CH=CHHtrans), 5.83 (ddt, 3Jd = 17.1, 3Jd = 10.2,
598.3326; found 598.3360 (∆
=
–5.8 ppm), calcd. for
3Jt = 6.7 Hz, 2 H, CH=CH2), 7.10 (mc with d, J = 8.9 Hz, 4 H, C3713CH4735ClN2O2: 599.3359; found 599.3358 (∆ = 0.3 ppm).
3
3,5-CArH), 7.73 (s, 2 H, 5,6-CPhenH), 8.08 (d, 3J = 8.4 Hz, 2 H, 3,8-
2,21,23,42-Tetraoxa-1,22(1,3,4)-dibenzena-43(2,9)-1,10-phenanth-
3
CPhenH), 8.25 (d, J = 8.4 Hz, 2 H, 4,7-CPhenH), 8.42 (mc with d,
rolina-bicyclo[20.20.1]tritetracontaphan-11,32-diene (24b): 2,9-
Bis[2,4-bis(dec-9-enyloxy)phenyl]-1,10-phenanthroline (21b, 30 mg,
32 µmol) was dissolved in dry dichloromethane (36 mL). After ad-
dition of benzylidene-bis(tricyclohexylphosphane)dichlororuthe-
nium (Grubbs type I catalyst, 3 mg, 4 µmol, 12 mol-%), the solu-
tion was stirred at room temp. under nitrogen for 18 h and was
then filtered through basic aluminium oxide. The solvent was evap-
orated in vacuo and the crude product was purified by chromatog-
raphy (Chromatotron, 2 mm, silica gel, cyclohexane/ethyl acetate,
2:1, Rf = 0.58) to yield a yellow oil (20 mg, 22 µmol, 71%). 1H
NMR (500 MHz, CDCl3): δ = 0.80–0.91 (m, 4 H, CH2), 0.95–1.03
(m, 4 H, CH2), 1.22–1.54 (m, 32 H, CH2), 1.77–1.87 (m, 8 H,
OCH2CH2), 1.94–2.09 (m, 8 H, CH2CH=), 4.05 (mc, 8 H, OCH2),
4.98 (mc, 1.46 H, CH=CHHcis#), 5.06 (mc, 0.54 H,
CH=CHHtrans#), 5.34 (mc, 1.2 H, CH=CHHcis*), 5.42 (mc, 0.8 H,
3J = 8.9 Hz, 4 H, 2,6-CArH) ppm. 13C NMR (150 MHz, CDCl3): δ
= 26.1, 29.0, 29.1, 29.3, 29.4, 29.5 (t, CH2), 33.8 (t, CH2CH=), 68.2
(t, OCH2), 114.2 (t, =CH2), 114.9 (d, 3,5-CAr), 119.3 (d, 3,8-CPhen),
125.6 (d, 5,6-CPhen), 127.5 (s, 4a,6a-CPhen), 129.0 (d, 2,6-CAr), 132.0
(s, 1-CAr), 136.8 (d, 4,7-CPhen), 139.2 (d, CH=CH2), 146.1 (s,
10a,10b-CPhen), 156.5 (s, 2,9-CPhen), 160.6 (s, 4-CAr) ppm. IR
(KBr): ν = 2936 (aliph. CH), 1603, 1458 (arom. C=C), 1246, 1034
˜
(C–O–C) cm–1. MS (EI, 70 eV): m/z (%) = 640 (100) [M]+, 515 (40)
[C35H35N2O2]+, 501 (36) [C34H33N2O2]+, 377 (17) [C25H17N2O2]+,
364 (72) [C24H15N2O2]+. MS (ESI, CHCl3/MeOH): m/z (%) = 641
(100) [M + H]+. HR-MS (EI, 70 eV): calcd. for C44H52N2O2:
640.4029; found 640.4029 (∆
C4313CH52N2O2: 641.4063; found 641.4062 (∆
C44H52N2O2 (640.40): calcd. 82.46, 8.18, N
=
0.1 ppm), calcd. for
0.1 ppm).
4.37.
=
C
H
C44H52N2O2·0.9C4H8O2 (640.40 + 79.25): calcd. C 79.38, H 8.29,
N 3.89; found C 79.38, H 8.21, N 3.79.
4
3
CH=CHHtrans*), 6.55 (d, J = 2.1 Hz, 2 H, 2-CArH), 6.74 (dd, J
4
≈ 8.6, J = 2.2 Hz, 2 H, 6-CArH), 7.74 (s, 2 H, 5,6-CPhenH), 8.16
3
3
(d, J = 8.4 Hz, 2 H, 4,7-CPhenH), 8.24 (d, J = 8.4 Hz, 2 H, 3,8-
CPhenH), 8.28 (d, 3J = 8.6 Hz, 2 H, 5-CArH) ppm. The assignments
marked with #, * may be reversed. 13C NMR (125 MHz, CDCl3):
δ = 25.7, 25.8, 28.2, 28.5, 28.7, 29.0, 29.1, 29.2, 29.4, 29.9 (d, CH2),
32.2 (d, CH2CH=), 32.5 (d, CH2CH=), 68.0 (d, OCH2), 68.1 (d,
CH2CH=), 100.6 (d, 2-CAr), 106.3 (d, 6-CAr), 123.5 (s, 1-CAr), 124.8
(d, 3,8-CPhen), 125.5 (d, 5-CAr), 126.9 (s, 4a,6a-CPhen), 129.7 (d, 5,6-
CPhen), 130.0 (d, CH=CH), 130.2 (d, CH=CH), 134.7 (d, 4,7-
CPhen), 146.1 (s, 10a,10b-CPhen), 156.3 (s, 2,9-CPhen), 158.2 (s, 3-
2-[2,4-Bis(dec-9-enyloxy)phenyl]-9-chloro-1,10-phenanthroline (23):
In an attempt to synthesise 2,9-bis[2,4-bis(dec-9-enyloxy)phenyl]-
1,10-phenanthroline (21b) from 2,9-dichloro-1,10-phenanthroline
(10, 200 mg, 803 µmol) by Suzuki coupling with crude 2,4-bis(dec-
9-enyloxy)phenylboronic acid (17b, 600 mg, ca. 1.4 mmol) in the
presence of tetrakis(triphenylphosphane)palladium(0) (57 mg,
47 µmol) and barium hydroxide octahydrate (670 mg, 2.11 mmol)
(reaction and workup conditions as described for the synthesis of
21b from diiodide 12), the monoarylated phenanthroline 23 was
isolated by chromatography (Chromatotron, 2 mm, silica gel,
dichloromethane/ethyl acetate, 4:1, Rf = 0.18) as a colourless oil
C
Ar), 161.0 (s, 4-CAr) ppm. IR (KBr): ν = 2924, 2851 (aliph. CH),
˜
1609, 1580, 1487 (arom. C=C), 1262, 1100, 1022 (COC), 801 (2
neighbouring arom. CH) cm–1. MS (ESI, CHCl3/MeOH): m/z (%)
= 893.6 (100) [M + H]+, 879.6 (40) [M + H – CH2]+. MS (EI,
70 eV): m/z (%) = 892 (11) [M]+, 799 (9) [M – C7H13]+, 97 (100)
[C7H13]+. HR-MS (ESI, CHCl3/MeOH): C60H80N2O4 (892.61),
calcd. for C60H80N2O4 + H+: 893.6191; found 893.6249 (∆ =
6.5 ppm), calcd. for C5913CH80N2O4 + H+: 894.6224; found
894.6182 (∆ = 4.7 ppm).
1
(95 mg, 159 µmol, 34%). H NMR (500 MHz, CDCl3): δ = 1.21–
1.52 (m, 20 H, CH2), 1.80 (mc, 4 H, OCH2CH2), 1.98 (mc, 2 H,
CH2CH=), 2.06 (mc, 2 H, CH2CH=), 4.02 (t, 3J ≈ 6.5 Hz, 2 H,
OCH2), 4.04 (t, 3J ≈ 6.5 Hz, 2 H, OCH2), 4.91 (ddt, 3Jd = 10.2 Hz,
2Jd = 2.2 Hz, 4Jt = 1.1 Hz, 1 H, CH=CHHcis), 4.94 (ddt, 3Jd
≈
2
4
10.2 Hz, Jd = 2.2 Hz, Jt = 1.2 Hz, 1 H, CH=CHHcis), 4.96 (ddt,
3Jd = 17.1 Hz, 2Jd = 2.1 Hz, 4Jt = 1.6 Hz, 1 H, CH=CHHtrans), 5.01
(ddt, 3Jd = 17.1 Hz, 2Jd = 2.0 Hz, 4Jt = 1.6 Hz, 1 H, CH=CHHtrans), 4,15-Dioxa-1,3(1,4)-dibenzena-2(2,9)-1,10-phenanthrolina-cyclopen-
5.78 (ddt, 3Jd = 17.0 Hz, 3Jd = 10.2 Hz, 3Jt = 6.7 Hz, 1 H,
tadecaphan-7-ene (25a): 2,9-Bis[4-(hex-5-enyloxy)phenyl]-1,10-
phenanthroline (22a, 80.0 mg, 152 µmol) was dissolved in dry
3
3
CH=CH2), 5.82 (ddt, 3Jd = 17.0 Hz, Jd = 10.2 Hz, Jt = 6.7 Hz, 1
H, CH=CH2), 6.56 (t, J = 2.3 Hz, 1 H, 3-CArH), 6.71 (dd, 3J = dichloromethane (160 mL) under nitrogen. After addition of
4
8.6 Hz, 4J = 2.3 Hz, 1 H, 5-CArH), 7.58 (d, 3J = 8.3 Hz, 1 H, 8-
benzylidene-bis(tricyclohexylphosphane)dichlororuthenium
CPhenH), 7.71 (d, 3J = 8.7 Hz, 1 H, 5-CPhenH), 7.80 (d, 3J = 8.7 Hz, (Grubbs type I catalyst, 14.5 mg, 18.5 µmol, 12 mol-%), the solu-
1 H, 6-CPhenH), 8.16 (d, 3J = 8.4 Hz, 1 H, 7-CPhenH), 8.17 (d, J = tion was stirred at room temp. for 7 d. TLC still showed starting
3
8.5 Hz, 1 H, 3-CPhenH), 8.29 (d, 3J = 8.6 Hz, 1 H, 6-CArH), 8.30 (d,
3J = 8.5 Hz, 1 H, 4-CPhenH) ppm. 13C NMR (150 MHz, CDCl3): δ
material, so benzylidene-bis(tricyclohexylphosphane)dichlororu-
thenium (Grubbs type I catalyst, 8.0 mg, 10 µmol, 7 mol-%) was
= 26.1 (d, CH2), 26.2 (d, CH2), 28.9 (d, CH2), 28.9 (d, CH2), 29.0 added again and the solution was stirred at room temp. for another
(d, CH2), 29.1 (d, CH2), 29.2 (d, CH2), 29.2 (d, CH2), 29.3 (d, 4 d. The solution was filtered through basic aluminium oxide and
CH2), 29.4 (d, CH2), 29.4 (d, CH2), 29.5 (d, CH2), 33.7 (d, the solvent was evaporated in vacuo. The crude product was par-
CH2CH=), 33.8 (d, CH2CH=), 68.2 (d, OCH2), 68.8 (d, OCH2),
100.4 (d, 3-CAr), 106.3 (d, 5-CAr), 114.1 (2ϫt, =CH2), 122.4 (s, 4-
CAr), 123.9 (d, 8-CPhen), 124.7 (d, 5-CPhen*), 125.5 (d, 6-CAr), 126.9
tially purified by chromatography (Chromatotron, 2 mm, silica gel,
cyclohexane/ethyl acetate, 2:1, Rf = 0.58) to yield several fractions
that contained both starting material and product. The characteri-
Eur. J. Org. Chem. 2009, 2328–2341
© 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
2339

F. Eggers, U. Lüning
FULL PAPER
sation of product 25a was carried out with the purest fraction; yield
4,23-Dioxa-1,3(1,4)-dibenzena-2(2,9)-1,10-phenanthrolina-cyclo-
tricosaphan-11-ene (25c): This compound was synthesised by the
procedure described above for 4,15-dioxa-1,3(1,4)-dibenzena-
40 mg as yellow oil (mixture of starting material and product); m.p.
1
220–226 °C. H NMR (600 MHz, CDCl3): δ = 1.45–1.57 (m, 4 H,
OCH2CH2CH2), 1.86 (mc, 4 H, OCH2CH2), 1.97–2.08 (m, 4 H, 2(2,9)-1,10-phenanthrolina-cyclopentadecaphan-7-ene (25a), from
3
3
CH2CH=), 4.09 (t, J = 6.7 Hz, 4 H, OCH2), 5.41 (t, J = 4.8 Hz,
2,9-bis[4-(dec-9-enyloxy)phenyl]-1,10-phenanthroline (22c, 105 mg,
164 µmol) and benzylidene-bis(tricyclohexylphosphane)dichlororu-
1 H, CH=CHcis*), 5.50 (mc, 1 H, CH=CHtrans*), 7.11 (mc with d,
3J = 8.9 Hz, 4 H, 3,5-CArH), 7.73 (s, 2 H, 5,6-CPhenH), 8.07 (d, J thenium (Grubbs type I catalyst, 10.2 mg, 13.0 µmol, 8 mol-%) in
3
= 8.5 Hz, 2 H, 3,8-CPhenH), 8.25 (d, 3J = 8.5 Hz, 2 H, 4,7-CPhenH),
dry dichloromethane (175 mL). The crude product was purified by
column chromatography (silica gel, cyclohexane/ethyl acetate, 2:1,
8.43 (mc, 4 H, 2,6-CArH) ppm. The assignments marked with * may
be reversed. 13C NMR (150 MHz, CDCl3): δ = 25.8 (t, CH2), 32.8 Rf = 0.26) to yield yellow crystals (35 mg, 57.2 µmol, 35%) m.p.
(t, OCH2CH2), 33.5 (t, CH2CH=), 67.9 (t, OCH2), 114.9 (d, 3,5- 101 °C. 1H NMR (100 MHz, CDCl3): δ = 1.33–1.43 (m, 16 H,
C
Ar), 119.2 (d, 3,8-CPhen), 125.5 (d, 5,6-CPhen), 127.5 (s, 4a,6a-
CH2), 1.51 (mc, 4 H, OCH2CH2CH2), 1.82–1.88 (m, 4 H,
OCH2CH2), 1.99–2.09 (m, 4 H, CH2CH=), 4.09 (t, J = 7.0 Hz, 4
3
CPhen), 129.0 (d, 2,6-CAr), 129.9 (d, CH=CH), 130.4 (d, CH=CH),
132.1 (s, 1-CAr), 136.7 (d, 4,7-CPhen), 146.1 (s, 10a,10b-CPhen), 156.4
H, OCH2), 5.37 (mc, 0.7 H, CH=CHcis*), 5.44 (mc, 1.3 H,
3
(s, 2,9-CPhen), 160.5 (s, 4-CAr) ppm. IR (KBr): ν = 2919 (aliph. CH),
CH=CHtrans*), 7.11 (mc with d, J = 8.7 Hz, 4 H, 3,5-CArH), 7.71
˜
1599, 1488 (arom. C=C), 1249, 1176 (C–O–C), 829 (1,4-disubst.
(s, 2 H, 5,6-CPhenH), 8.05 (mc with d, 3J = 8.3 Hz, 2 H, 3,8-CPhenH),
8.22 (d, 3J = 8.4 Hz, 2 H, 4,7-CPhenH), 8.43 (mc, 4 H, 2,6-
benzene) cm–1. MS (EI, 70 eV): m/z (%) = 500 (100) [M]+, 364 (21)
[M – C10H15]+. MS (ESI, CHCl3/MeOH): m/z (%) = 523 (17) [M CArH) ppm. The assignments marked with * may be reversed. 13C
+ Na]+, 501 (100) [M + H]+. HR-MS (EI, 70 eV): m/z (%) calcd.
for C34H32N2O2: 500.2464; found 500.2463 (∆ = 0.1 ppm), calcd.
for C3313CH32N2O2: 501.2497; found 501.2495 (∆ = 0.2 ppm).
NMR (150 MHz, CDCl3): δ = 25.9, 26.0, 27.4, 28.6, 29.1, 29.3,
29.5 (t, CH2), 30.0 (t, OCH2CH2), 32.5 (t, CH2CH=), 68.1 (t,
OCH2), 114.9 (d, 3,5-CAr), 119.2 (d, 3,8-CPhen), 125.5 (d, 5,6-CPhen),
C34H32N2O2 (500.25): calcd.
C
81.57,
H
6.44,
N 5.11. 127.5 (s, 4a,6a-CPhen), 129.0 (d, 2,6-CAr), 129.9 (d, CH=CH), 130.4
C34H32N2O2·1 H2O·0.2CHCl3 (500.25 + 18.01 + 23.87): calcd. C
(d, CH=CH), 132.1 (s, 1-CAr), 136.7 (d, 4,7-CPhen), 146.1 (s,
75.71, H 6.32, N 5.16; found 75.55, H 6.38, N 4.88.
10a,10b-CPhen), 156.4 (s, 2,9-CPhen), 160.5 (s, 4-CAr) ppm. IR
(KBr): ν = 2924 (aliph. CH), 1654, 1564, 1459 (arom. C=C), 1247,
˜
4,19-Dioxa-1,3(1,4)-dibenzena-2(2,9)-1,10-phenanthrolina-cyclo-
nonadecaphan-9-ene (25b): This compound was synthesised by the
procedure described above for 4,15-dioxa-1,3(1,4)-dibenzena-
2(2,9)-1,10-phenanthrolina-cyclopentadecaphan-7-ene (25a) from
2,9-bis[4-(oct-7-enyloxy)phenyl]-1,10-phenanthroline (22b, 66 mg,
113 µmol) and benzylidene-bis(tricyclohexylphosphane)dichlororu-
thenium (Grubbs type I catalyst, 7 mg, 9 µmol, 8 mol-%) in dry
dichloromethane (120 mL). After filtration through basic alumin-
ium oxide, the crude product (30 mg, 51 µmol) was analysed by
ESI-MS. The ring-closing metathesis was not fully accomplished,
so the crude product was again dissolved in dichloromethane
(60 mL) and, after addition of benzylidene-bis(tricyclohexylphos-
phane)dichlororuthenium (Grubbs type I catalyst, 4 mg, 5 µmol,
10 mol-%), stirred for 3 d. Filtration through basic aluminium ox-
ide was followed by evaporation of the solvent in vacuo to yield
yellow crystals (25 mg, 45 µmol, 87%). 1H NMR (500 MHz,
CDCl3): δ = 1.36–1.54 (m, 12 H, CH2), 1.85 (mc, 4 H, OCH2CH2),
1014 (C–O–C), 834 (1,4-disubst. benzene) cm–1. MS (EI, 70 eV):
m/z (%) = 612 (94) [M]+, 569 (12) [C40H45N2O2]+, 515 (24)
[C35H35N2O2]+, 377 (42) [C25H17N2O2]+, 365, 364 (51, 100)
[C24H16N2O2]+. HR-MS (EI, 70 eV): C42H48N2O2, calcd. 612.3716;
found 612.3716 (∆ = 0 ppm), C4113CH48N2O2, calcd. 613.3749;
found 613.3746 (∆ = 0.6 ppm).
Cyclopropanation: Under argon, copper(I) triflate hemibenzene
complex (ca. 2.0 to 3.5 mg, +/–0.01 mg) was placed in a vial, and
indene [28, 440 equiv. based on copper(I)], and the ligands 1b, 2a,
3b or 4a–c (1.2 equiv.) dissolved in 1,2-dichloroethane (c =
0.01 mol L–1) were added. After addition of ethyl diazoacetate (26,
50 equiv.), the mixture was stirred at room temp. for 24 h. At the
beginning of the reaction, quick evolution of gas was frequently
noticed. After filtration of the mixture through silica gel with di-
ethyl ether as eluent, most of the solvent mixture was evaporated
in vacuo until ca. 5 mL remained. 1,2-Dichloroethane was added
to give ca. 10 mL of solution. After addition of n-hexadecane (ca.
25 mg, +/–0.01 mg) as GC standard, the products were analysed by
GC: HP-5, 30 mϫ320 µmϫ0.25 µm, 80 °C for 5 min, 10 °Cmin–1
until 140 °C, 1 min, 2 °Cmin–1 until 160 °C, 1 min, 20 °Cmin–1 un-
til 240 °C, 20 min.
3
2.02–2.12 (m, 4 H, CH2CH=), 4.15 (mc with t, J = 7.0 Hz, 4 H,
OCH2), 5.39 (mc, 0.7 H, CH=CHcis*), 5.45 (mc, 1.3 H,
CH=CHtrans*), 7.11 (mc, 4 H, 3,5-CArH), 7.71 (s, 2 H, 5,6-CPhenH),
8.04 (d, 3J = 8.3 Hz, 2 H, 3,8-CPhen), 8.23 (d, 3J = 8.4 Hz, 2 H, 4,7-
CPhenH), 8.39 (mc with d, 3J = 8.8 Hz, 4 H, 2,6-CArH) ppm. The
assignments marked with * may be reversed. 13C NMR (150 MHz,
CDCl3): δ = 25.7, 27.5, 28.3, 28.4, 29.1, 29.6 (t, CH2), 30.1 (t,
OCH2CH2), 32.5 (t, CH2CH=), 68.2 (t, OCH2), 115.3 (d, 3,5-CAr),
119.3 (d, 3,8-CPhen), 125.5 (d, 5,6-CPhen), 127.4 (s, 4a,6a-CPhen),
129.0 (d, 2,6-CAr), 129.4 (d, CH=CH), 130.5 (s, 1-CAr), 136.6 (d,
4,7-CPhen), 146.1 (s, 10a,10b-CPhen), 156.4 (s, 2,9-CPhen), 160.2 (s,
Acknowledgments
We warmly thank Dipl.-Chem. Dennis Stoltenberg for the prepara-
tion of 15f.
4-CAr) ppm. IR (KBr): ν = 2929 (aliph. CH), 1512, 1381 (arom.
˜
[1] See textbooks of biochemistry, e.g., D. Voet, J. G. Voet, C. W.
Pratt, Lehrbuch der Biochemie, Wiley-VCH, Weinheim, 2002.
[2] Concave geometry is a major factor in host–guest recognition.
Most molecules are “potato shaped” and thus convex. In order
to be complementary to such a molecule as a guest, host mole-
cules have to exhibit concave areas. For references see books
on supramolecular chemistry, for instance refs.[3–5]
[3] J. L. Atwood, J. W. Steed (Eds.), Encyclopedia of Supramolec-
ular Chemistry, Marcel Dekker, New York, 2004.
[4] J. W. Steed, J. L. Atwood, Supramolecular Chemistry, John
Wiley & Sons, Chichester, New York, Weinheim, Brisbane, Sin-
gapore, Toronto, 2000.
C=C), 1260, 1107, 1024 (C–O–C) cm–1. MS (ESI, CHCl3/MeOH):
m/z (%) = 557 (100) [M + H]+. MS (EI, 70 eV): m/z (%) = 556
(100) [M]+, 364 (99) [C24H14N2O4]+. HR-MS (ESI, CHCl3/MeOH):
C38H40N2O2 (556.31) calcd. for C38H40N2O2 + H+: 557.3163;
found 557.3142 (∆ = 3.8 ppm), calcd. for C3713CH40N2O2 + H+:
558.3195; found 558.3191 (∆ = 0.7 ppm). HR-MS (EI, 70 eV):
calcd. for C38H40N2O2: 556.3090; found 556.3078 (∆ = 2.2 ppm),
calcd. for C3713CH40N2O2: 557.3123; found 557.3117 (∆
=
1.1 ppm).
2340
www.eurjoc.org
© 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 2009, 2328–2341

Concave 1,10-Phenanthrolines as Ligands for Cyclopropanations
[5] J.-M. Lehn, Supramolecular Chemistry, VCH, Weinheim, New
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[6] U. Lüning, Liebigs Ann. Chem. 1987, 949–955.
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ing, M. Keller, Chem. Ber. 1994, 127, 2297–2306.
[8] M. Hagen, U. Lüning, Chem. Ber./Recueil 1997, 130, 231–234.
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[11] F. Löffler, M. Hagen, U. Lüning, Synlett 1999, 1826–1828.
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[13] U. Lüning, M. Müller, Chem. Ber. 1990, 123, 643–645.
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Received: December 18, 2008
Published Online: March 23, 2009
Eur. J. Org. Chem. 2009, 2328–2341
© 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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