Enantiopure Chiral Concave 1,10-Phenanthrolines

Article abstract of DOI:10.1002/ejoc.201501289

Chiral information has been introduced into concave 1,10-phenanthrolines of different ring sizes by using a 2,7-disubstituted naphthalene bridgehead, which causes axial chirality. A tetraphenolic 2-(dihydroxynaphthyl)-9-(dihydroxyphenyl)-1,10-phenanthroline was synthesized as a key intermediate. Two strategies were followed to obtain the bimacrocyclic chiral concave 1,10-phenanthrolines: quadruple Williamson ether synthesis or alkenylation of the OH groups and subsequent ring-closing metathesis followed by hydrogenation. The overall yields of bimacrocyles 19 were 10 to 17 % starting from the respective Suzuki coupling of the substituted arenes 11 and 13 to 2,9-dichloro-1,10-phenanthroline (5). Racemic mixtures of the three concave 1,10-phenanthrolines 19 were separated by using chiral high-performance liquid chromatography (HPLC) techniques, and their absolute stereochemistry was assigned by comparison of simulated and experimental circular dichroism (CD) spectra. The enantiopure concave 1,10-phenanthrolines were used as ligands in a copper-catalysed cyclopropanation, and their selectivity was determined by chiral gas chromatography (GC).

Full text of DOI:10.1002/ejoc.201501289

DOI: 10.1002/ejoc.201501289
Full Paper
Concave Reagents
Enantiopure Chiral Concave 1,10-Phenanthrolines[‡]
Lisa M. Reck,[a] Gebhard Haberhauer,[b] and Ulrich Lüning*[a]
Abstract: Chiral information has been introduced into concave respective Suzuki coupling of the substituted arenes 11 and 13
1,10-phenanthrolines of different ring sizes by using a 2,7-di- to 2,9-dichloro-1,10-phenanthroline (5). Racemic mixtures of
substituted naphthalene bridgehead, which causes axial chiral- the three concave 1,10-phenanthrolines 19 were separated by
ity. A tetraphenolic 2-(dihydroxynaphthyl)-9-(dihydroxyphenyl)- using chiral high-performance liquid chromatography (HPLC)
1,10-phenanthroline was synthesized as a key intermediate. techniques, and their absolute stereochemistry was assigned by
Two strategies were followed to obtain the bimacrocyclic chiral comparison of simulated and experimental circular dichroism
concave 1,10-phenanthrolines: quadruple Williamson ether syn- (CD) spectra. The enantiopure concave 1,10-phenanthrolines
thesis or alkenylation of the OH groups and subsequent ring- were used as ligands in a copper-catalysed cyclopropanation,
closing metathesis followed by hydrogenation. The overall and their selectivity was determined by chiral gas chromatogra-
yields of bimacrocyles 19 were 10 to 17 % starting from the phy (GC).
Introduction
Numerous chemical transformations are carried out selectively
with the help of enzymes in the living cell.[1] An important fea-
ture for this selectivity is geometry. The catalytic functionalities
are embedded in a specially shielded area of the respective
protein: the active site. Concave reagents (see Figure 1) copy
Figure 1. The geometry of a concave reagent resembles that of a light bulb
in a lampshade with the light bulb being the active centre and the shade
being the concave shielding. One class of such concave reagents are the
concave 1,10-phenanthrolines. They are built up by attaching two bridge-
this geometry by incorporating a catalytic centre into a bi-
macrocycle.[2–4] Previous work has shown that the chemo-,[5]
regio-[6] and stereoselectivity[7] of catalytic reactions can be
controlled by using bimacrocyclic concave reagents.
heads to positions 2 and 9 of 1,10-phenanthroline and then connecting the
ortho-positions of the bridgeheads to yield a bimacrocyclic concave 1,10-
phenanthroline (X, Y = polymethylene or polyethylene glycol).[8]
To also control enantioselectivity[9] – as enzymes do due to
their chiral structure – concave reagents have to be enantio-
merically pure. There are several ways of introducing chiral in-
formation into a catalyst. Often, chiral substituents are attached;
however, a problem emerges in the case of concave reagents. If
a chiral substituent was attached to these usually bimacrocyclic
reagents, an attachment at the outside of the bimacrocycle
would normally have little influence on the active site in the
interior. However, if a substituent was attached on the inside,
the cavity would be filled and the substrates would no longer
be able to approach the catalytic site.
formed by introducing axial chirality by using nonsymmetric
bridgeheads in the bimacrocycle. This approach has been suc-
cessful for concave N-heterocyclic carbenes (NHC).[10] By ex-
changing one of the usual phenyl bridgeheads for a naphthal-
ene, a chiral NHC precursor (Figure 2) was synthesized. By chro-
matography,[11,12] separation of the enantiomers was possi-
ble.[13]
Therefore, we have chosen a different approach and have
designed the whole molecule asymmetrically. This can be per-
[‡] Concave Reagents, 66. Part 65: T. Liebig, U. Lüning, Synthesis 2014, 46,
2799–2807
[a] Otto-Diels-Institut für Organische Chemie, Christian-Albrechts-Universität
zu Kiel,
Figure 2. Configurationally stable chiral concave NHC precursor.[13]
Olshausenstraße 40, 24098 Kiel, Germany
E-mail: luening@oc.uni-kiel.de
http://www.luening.otto-diels-institut.de/de
[b] Institut für Organische Chemie, Universität Duisburg-Essen,
Universitätsstraße 7, 45117 Essen, Germany
E-mail: gebhard.haberhauer@uni-due.de
In this work, we have adopted this strategy for the synthesis
of chiral concave 1,10-phenanthrolines, which contain two
nitrogen atoms. A concave 1,10-phenanthroline may react as a
base or a base catalyst but even more as a chelating ligand for
transition-metal ions. There are numerous reactions that may
Supporting information for this article is available on the WWW under
http://dx.doi.org/10.1002/ejoc.201501289.
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be catalyzed by complexes of 1,10-phenanthrolines. In the past,
we have been able to improve the diastereoselectivity of cyclo-
propanations up to >99:1 by the concave shielding in concave
1,10-phenanthrolines.[7] In addition, with enantiomerically pure
concave 1,10-phenanthrolines, enantioselectivity can be ex-
pected in these catalyses.
Results and Discussion
Two slightly different pathways have previously been devel-
oped to synthesize concave 1,10-phenanthrolines: the first in-
volves a tetraphenol as intermediate and uses a quadruple Willi-
amson ether synthesis to build up the macrocycle.[8] The sec-
ond approach connects bridgeheads carrying alkenyl substitu-
ents to the phenanthroline by Suzuki couplings first, followed
by ring-closing metathesis and hydrogenation. Although the
second route requires more steps, the overall yields were bet-
ter.[14]
To transfer this second approach to chiral concave 1,10-
phenanthrolines, a 2,7-dialkenylated naphthaleneboronic acid 3
or the respective pinacol ester of the boronic acid 4, needed to
be synthesized (Scheme 1).
Scheme 2. Synthesis of tetraalkenylated 1,10-phenanthroline 8 by Suzuki cou-
plings. Reagents and conditions: (a) synthesized according to a reported pro-
cedure,[15] 66 %; (b) Method A: 3, Pd(PPh3)4, Ba(OH)2, 1,2-dimethoxy-
ethane, H2O, 65 %; (c) Method B: 4, Pd(OAc)2, 1,3-bis(diphenylphosphan-
yl)propane (dppp), Ba(OH)2, 1,2-dimethoxyethane, H2O, 64 %.
phenolic naphthyl-phenyl-1,10-phenanthroline 16. Benzyl
groups were chosen as protecting groups for the phenolic OH
groups. Scheme 3 summarises the syntheses of benzyl pro-
tected phenylboronic acid 11 and naphthylboronic ester 13,
which were synthesized from the respective bromides 10 and
12.
Scheme 1. Synthesis of the 2,7-dialkenylated naphthalene building blocks 3
and 4 (Pin = OCMe2CMe2O). Reagents and conditions: (a) 5-hexen-1-ol, PPh3,
diisopropyl azodicarboxylate (DIAD), THF, 74 %; (b) 1. nBuLi, THF; 2. B(OMe)3;
3. H2O, crude product; (c) 1. nBuLi, THF; 2. B(OMe)3; 3. pinacol, 79 %.
Respective boronic acids or esters can be coupled with 2,9-
dihalogeno-1,10-phenanthrolines.[15,16] By using one equivalent
of phenylboronic acid 6 (accessed through the Mitsunobu reac-
tion; see the Supporting Information) first and subsequently
one equivalent of a respective naphthalene derivative 3 or 4,
the tetraalkenylated 1,10-phenanthroline 8 was synthesized in
43 or 42 % overall yield, respectively (Scheme 2).
After isolation of product 8, NMR spectroscopic data showed
that an isomerization of the terminal alkenyl groups from termi-
nal to internal alkenes (10–20 %) had occurred during the Su-
zuki coupling reaction of the naphthyl building block. This was
confirmed by subsequent ring-closing metathesis, after which
MS spectroscopy showed additional smaller bimacrocycles.
Considering that a mixture of bimacrocycles of different ring
sizes would be an obstacle to the enantioseparation of the final
products and, moreover, because the stereoselective effect of
the macrocycles in the cyclopropanation reaction was to be
Scheme 3. Generation of aryl boronic acid 11 and boronic ester 13 (Pin =
OCMe2CMe2O), precursors of the bridgeheads in the concave 1,10-phen-
anthrolines: Reagents and conditions: (a) benzyl bromide, K2CO3, acetone,
92 %; (b) 1. nBuLi, THF; 2. B(OMe)3; 3. H2O, 54 %; (c) benzyl bromide, K2CO3,
acetone, 72 %; (d) 1. nBuLi, THF; 2. isopropoxyboronic acid pinacol ester,
51 %.
Using building blocks 11 and 13, tetrabenzyl ether 15 could
be synthesized by first coupling the phenyl moiety to position
2 (14, 59 %) and then the naphthyl unit to position 9 of 1,10-
phenanthroline (15, 57 %; Scheme 4). Hydrogenation with pal-
ladium as catalyst gave tetraphenol 16 in 94 % yield.
Quadruple Williamson ether syntheses with 5-bromo-1-pent-
examined in relation to their ring sizes, alkene isomerization ene or 6-bromo-1-hexene gave the respective precursors 17
had to be avoided. Therefore, we decided to introduce the and 8 (81 % each) for ring-closing metatheses. Double ring-
alkene moieties later in the synthesis by alkylation of a tetra- closure was performed with Grubbs' catalyst I in dichloro-
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Scheme 4. Concave 1,10-phenanthrolines 19 can be prepared from tetraphenol 16. Reagents and conditions: (a) Pd(PPh3)4, Na2CO3, 1,2-dimethoxyethane,
H2O, 59 %; (b) 13, Pd(dppf)Cl2, Ba(OH)2, 1,2-dimethoxyethane, H2O, 57 %; (c) H2, Pd(OH)2/C, Pd/C, EtOAc, 94 %; (d) 5-bromo-1-pentene or 6-bromo-1-hexene,
Cs2CO3, DMSO, 81 %; (e) Grubbs type I catalyst, CH2Cl2, rac-18a 78 %, rac-18c 84 %; (f) H2, Pd/C, EtOAc, CH2Cl2, rac-19a 76 %, rac-19c 80 %; (g) 1,9-dibromo-
nonane, Cs2CO3, K2CO3, DMF, rac-19b 31 %.
methane, and bimacrocyclic 1,10-phenanthrolines rac-18a and
rac-18c were obtained as E/Z mixtures in 78 and 84 % yield,
respectively. The final step of the synthetic sequence
(Scheme 4) was the hydrogenation of the double bonds, in
which all E or Z isomers were transformed into the same satu-
rated products rac-19a (76 %) or rac-19c (80 %).
With this approach, homolog free bimacrocycles with an
even number of CH2 groups in the alkylene chains (rac-19a: n =
8, rac-19c: n = 10) could be synthesized in 100–200 mg
amounts. For rac-19b, with an odd number of CH2 groups (n =
9), a different route had to be chosen. Nonamethylene chains
were directly introduced by Williamson ether syntheses using
1,9-dibromononane as bridging reagent under high dilution
conditions. rac-19b was isolated in 31 % yield.
The racemic mixtures of the three bimacrocycles rac-19 were
then separated by chiral HPLC to give the enantiopure com-
pounds (Figure 3).
For characterization and determination of the absolute con-
figuration of the enantiopure bimacrocycles 19, circular di-
chroism (CD) spectra were recorded. Figure 4 shows the CD
spectra of the smallest bimacrocycles 19a. Between 200 and
350 nm, four Cotton effects could be observed. The largest Cot-
Figure 3. Chiral HPLC chromatograms of (A) rac-19a [tR = 25.3 (M), 28.1
(P) min]; (B) rac-19b [tR = 28.7 (M), 32.8 (P) min]; (C) rac-19c [tR = 29.8 (M),
33.8 (P) min]. For experimental details, see experimental section.
ton effect was measured at 230 nm with a negative maximal
polarization of –169 mol–1 dm cm–1 for enantiomer (M)-19a and
The absolute configuration could be determined by compar-
a positive maximal polarization of +156 mol–1 dm3 cm–1 for ing the recorded spectra of the bicyclic 1,10-phenanthrolines
enantiomer (P)-19a.[17] Thus, the expected mirrored shape of 19a with the calculated CD spectrum of the M-isomer of 19a.
the polarization of the two enantiomers could be observed.
For this purpose, the structure of (M)-19a was optimized by
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Figure 4. Recorded CD spectra of 19a in MeCN [c((M)-19a) = 0.451 m
19a) = 0.378 m ].
M, c((P)-
Figure 6. Recorded CD spectra of 19b in MeCN [c((M)-19b) = 0.334 mM, c((P)-
19b) = 0.371 mM].
M
means of B3LYP-D3[18,19] calculations using the 6-31G*[20] basis
set. Subsequently, the CD spectrum of (M)-19a was simulated
with the time-dependent density functional theory (TD-DFT)
using the B3LYP functional and the 6-31G* basis set. No solvent
model was taken into account for the calculation of the spec-
trum. A comparison of the simulated CD spectrum of (M)-19a
(Figure 5) with the measured CD spectrum of 19a (Figure 4),
which shows a minimum at 230 nm and maxima at 242 and
266 nm, reveals that the corresponding compound represents
the M-isomer.
Figure 7. Recorded CD spectra of 19c in MeCN [c((M)-19c) = 0.398 m
19c) = 0.300 m ].
M, c((P)-
M
Table 1. Optical rotations of the different concave enantiomers measured in
acetonitrile.
19a
19b
19c
[α]D20(M)-isomer [°mL dm–1 g–1
Concentration [m
[α]D20 (P)-isomer [°mL dm–1 g–1
Concentration [m
]
+495°
0.43
–500°
0.45
+466°
0.54
–434°
0.37
+320°
0.52
–314°
0.42
M
]
]
M]
Figure 5. Simulated CD spectrum of (M)-19a using TD-DFT-B3LYP/6-31G*.
The recorded CD spectra of the larger bicyclic 1,10-phen-
anthrolines 19b and 19c are very similar to those of 19a. As diastereomeric cyclopropanes anti-22 and syn-22 with their re-
their structures only differ in length changes of the oligometh- spective enantiomers).
ylene chains by one or two methylene groups, the assignment
of the enantiomers can be executed in analogy to 19a (Figure 6
and Figure 7).
In addition to the cyclopropanation, a side reaction between
two molecules of EDA 20 can occur, which leads to the forma-
tion of the diastereomers diethyl fumarate (23) and diethyl mal-
For complete characterization, the specific optical rotations eate (24) (Scheme 6).
of all enantiomers were determined as listed in Table 1.
The reaction was carried out with the respective M-enan-
Finally, the stereoselective effect of the enantiopure concave tiomers of the bicyclic 1,10-phenanthrolines 19. The results
1,10-phenanthrolines 19 as ligands in the copper(I) catalyzed were compared to the cyclopropanations without any ligand
cyclopropanation reaction of indene[21] (21) with ethyl diazo- and in the presence of the acyclic 1,10-phenanthroline 30,
acetate (EDA, 20) was examined.[22] In this reaction, four stereo- which was synthesized in analogy to 1,10-phenanthroline 15
isomers of cyclopropane 22 (Scheme 5) can be formed (the (Scheme 7).
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Table 2. Diastereomeric and enantiomeric ratios and overall yields of the
cyclopropanes 22 measured by chiral GC. The absolute configuration of the
enantiomers was not assigned. E1 and E2 correlate with the respective reten-
tion times in the gas chromatograms.
Ligand
syn/anti
syn-E1/E2
anti-E1/E2
Yield (%)
–
30
19a
19b
19c
26:74
15:85
54:46
61:39
28:72
48:52
50:50
53:47
47:53
37:63
50:50
50:50
55:45
60:40
77:23
39
25
19
26
37
Scheme 5. Cyclopropanation of indene (21) by ethyl diazoacetate (20) yields
four products, two diastereomeric pairs of enantiomers anti-22 and syn-22.
(a) Copper(I) triflate, ligands.
Table 3. Ratios and overall yields of the side products diethyl fumarate (23)
and diethyl maleate (24) observed in the cyclopropanation of indene (21)
with EDA (20), measured by GC.
Ligand
23/24
Yield (%)
–
30
19a
19b
19c
59:41
66:34
31:69
29:71
35:65
10
9
10
8
Scheme 6. Side reaction of the cyclopropanation of alkenes by ethyl diazo-
acetate (20): dimerization of the carbene subunit to give diethyl fumarate
(23) and diethyl maleate (24). (a) Copper(I) triflate, ligand.
9
without any ligand present. The smaller ligands 19a and 19b
even favored the syn-product (syn-22), albeit with little selectiv-
ity.
Concerning enantioselectivity, the largest chiral phenanthrol-
ine 19c performed best, with ratios of enantiomers of approxi-
mately 1:2 (syn-22 E1/E2) and 1:3 (anti-22 E1/E2). The other li-
gands 19a, 19b and of course 30 did not influence the enantio-
selectivity of syn-22 E1/E2 in a significant way (ee determina-
tions possess an error of at least 2–3 %). However, for anti-22
E1/E2, an increasing enantioselectivity could be observed with
increasing ring size.
The side reaction in copper(I) catalyzed cyclopropanations is
the reaction of the copper carbenoid – formed by reaction of a
first molecule of diazoacetate with the copper(I) ion followed
by expulsion of nitrogen – with a second molecule of diazo-
acetate instead of the alkene, leading to the formation of dia-
stereomeric fumarates (23) and maleates (24) (Scheme 6). The
E/Z selectivity of the formation of these two alkenes 23 and 24
is also influenced by the nature of the ligands bound to the
copper(I) ions. Without any ligand or in the presence of non-
macrocyclic ligand 30, E-selectivity (i.e., the preferred formation
of fumarate 23) was found. Previously, a preference for the E-
isomer was found for most concave 1,10-phenanthrolines.[7]
Only a calixarene-based 1,10-phenanthroline[23] showed re-
versed selectivities,[7] both for the formation of maleate and
fumarate but also in the cyclopropanations themselves. A com-
Scheme 7. Synthesis of reference substance 30: Reagents and conditions:
(a) Me2SO4, KOH, H2O, 53 %; (b) NBS, LiClO4·SiO2, CH2Cl2, 81 %; (c) 1. nBuLi,
THF, 2. isopropoxyboronic acid pinacol ester, 74 %; (d) Pd(dppf)Cl2, Ba(OH)2,
1,2-dimethoxyethane, H2O, 42 %.
The results of the cyclopropanation reactions, which were
carried out as batch reactions, are shown in Table 2 and Table 3.
Concerning syn/anti-diastereoselectivity for the formation of bined experimental and theoretical investigation suggested a
the cyclopropanes 22, the nonchiral, acyclic ligand 30 showed different orientation of the reaction partners in symmetric con-
the best selectivity in favor of the anti-cyclopropane anti-22. By cave 1,10-phenanthrolines and in distorted bridged calix-
comparison with experiments in which nonchiral concave 1,10- arenes.[24] The reversed E/Z-selectivities for the fumarate/male-
phenanthrolines were used,[7] anti-selectivity was expected ate formation and the small anti-selectivity (smaller than in the
(syn-/anti-ratios up to <1:99). But the chiral concave 1,10- absence of any ligand) in the cyclopropanation of indene in the
phenanthrolines 19 showed less pronounced diastereoselectivi- reactions with chiral concave 1,10-phenanthrolines 19 as li-
ties. In contrast, only the largest bimacrocycle 19c led to a pre- gands suggest distorted transition states, which may resemble
ferred formation of the anti-cyclopropane anti-22 with an those in the calixarene case, especially for the smaller chiral
syn/anti-diastereoselectivity similar to the cyclopropanation concave 1,10-phenanthrolines 19a and 19b.
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tra: for assignment of the signals, “phen” for phenanthroline, “naph”
for naphthyl, “ar” for phenyl, and “bn” for benzyl are used. In the
case of the bimacrocyclic 1,10-phenanthrolines 18 and 19, aromatic
signals were assigned in analogy to the acyclic precursors, to allow
better comparison. EI/CI mass spectra were recorded with a Finni-
gan MAT 8200 and MAT 8230. ESI mass spectra were recorded with
an Applied Biosystems Mariner Spectrometry Workstation. MALDI-
TOF mass spectra were recorded with a Bruker-Daltronics Biflex III
with Cl-CCA (4-chloro-α-cyano-cinnamic acid) as matrix. HRMS were
recorded with a Bruker-Daltronics APEX 3 FT-ICR mass spectrometer
(7.05 T, ESI, CH2Cl2/MeOH/HCOOH). IR spectra were recorded with
a Perkin–Elmer Spectrum 100 spectrometer equipped with an MKII
Golden GateTM Single Reflection ATR unit. Elemental analyses were
carried out with a Euro EA 3000 Elemental Analyzer from Euro Vec-
tor. Preparative separation of the enantiomers of 19 was conducted
with a VWR-Hitachi HPLC-system Elite LaChrom (L-2130 pump sys-
tem, L-2400 UV-detector) connected to a Waters In-Line degasser
AF, a Waters 717plus autosampler and a Foxy R1 fraction collector.
A 8 × 250 mm DELTA-RP S column (Macherey–Nagel) protected by
a 8 × 10 mm guard column of the same material was used. The
chiral separation was achieved by elution with acetonitrile/water/
triethylamine (80:20:0.1) with a flow rate of 3 mL/min. The CD Spec-
tra of 19 were recorded with a Jasco J-720 CD spectrometer. The
specific optical rotation was measured with a Perkin–Elmer Polarim-
eter 241 at 589.3 nm. The analyses of the cyclopropanation reac-
tions were conducted with a Varian 3400 gas chromatograph using
a 25.0 m × 250 μm Hydrodex-ꢀ-PM column (Macherey–Nagel,
Tcolumn = 120 °C), helium as carrier gas (10 psi), and a Varian 4290
Integrator.
Conclusions
Chiral concave 1,10-phenanthrolines 19a–c of different ring
sizes have been synthesized. First, two bridgeheads were added
to 2,9-dichloro-1,10-phenanthroline (5) by Suzuki couplings
with bis(benzyloxy)phenylboronic acid 11 and bis(benzyl-
oxy)naphthyl boronic acid pinacol ester 13. Next, the oxygen
substituents were deprotected. Double ring-closure formed the
bimacrocycles 19a–c either by fourfold Williamson ether syn-
thesis or by attaching alkenyl groups, followed by double ring-
closing metathesis and hydrogenation of the remaining double
bonds. The overall yields of rac-19a–c were 10–17 %. The enan-
tioseparation of the racemic mixtures was possible using chiral
HPLC. Absolute configuration could be determined by compar-
ing experimental and simulated CD spectra of (M)-19a. First
investigations of the stereoselective influence of (M)-19a–c as
ligands in the copper(I)-catalyzed cyclopropanation reaction of
indene (21) with ethyl diazoacetate (EDA, 20) were carried out.
The use of the largest chiral concave 1,10-phenanthroline 19c
led to the highest diastereo- and enantioselectivities. Further
investigations have to be made to fully understand the ob-
served selectivities.
Experimental Section
General Remarks: The following chemicals were obtained com-
mercially and used without further purification: basic aluminium
oxide (Macherey–Nagel), benzyl bromide (ABCR), benzylidene-
bis(tricyclohexylphosphine)dichlororuthenium (Grubbs type I cata-
1-Bromo-2,7-bis(hex-5-enyloxy)naphthalene (2): Under nitrogen,
1-bromo-2,7-dihydroxynaphthalene (1; 2.54 g, 10.6 mmol), 5-hexen-
lyst; Aldrich), [1,1′-bis(diphenylphosphanyl)ferrocene]dichloropalla- 1-ol (3.83 mL, 3.19 g, 31.9 mmol) and triphenylphosphine (5.58 g,
dium(II) (ABCR), 1,3-bis(diphenylphosphanyl)propane (Aldrich), 6-
bromo-1-hexene (Matrix Scientific), 5-bromo-1-pentene (Matrix
Scientific), n-butyllithium (Aldrich), Celite (Sigma–Aldrich), copper(I)
triflate benzene complex (Aldrich), 1,9-dibromononane (ABCR), 2,7-
21.3 mmol) were dissolved in anhydrous tetrahydrofuran (55 mL).
The solution was cooled to 0 °C and diisopropyl azodicarboxylate
(6.70 mL, 6.43 g, 31.9 mmol) was added slowly. The solution was
then stirred at room temp. for 19 h. The reaction mixture was hydro-
dihydroxynaphthalene (25, Merck), diisopropyl azodicarboxylate lyzed with water (31 mL), then sodium hydroxide solution (2
(Alfa Aesar), dimethyl sulfate (Sigma–Aldrich), dimethyl sulfoxide 8 mL) was added. After stirring for 30 min and separation of the
(anhydrous, Sigma–Aldrich), ethyl diazoacetate (Aldrich, contains layers, the aqueous layer was extracted twice with diethyl ether.
≥ 13 wt.-% dichloromethane), 5-hexen-1-ol (Alfa Aesar), indene (Al- The combined organic layer was washed with brine and dried with
drich), isopropoxyboronic acid pinacol ester (ABCR), lithium per- magnesium sulfate. The solvents were evaporated and the residue
chlorate (Sigma–Aldrich), N-bromosuccinimide (Merck), N,N-dimeth- was dissolved in dichloromethane (15 mL). Cyclohexane (200 mL)
M,
ylformamide (anhydrous; Sigma–Aldrich), palladium diacetate (in- was added and the mixture was cooled to 1 °C overnight. The pre-
house chemical supply), palladium on charcoal (10 %; ABCR), Pearl- cipitated triphenylphosphine oxide was filtered off and washed
mans catalyst [20 % Pd(OH)2 on charcoal (50 % water); Alfa Aesar],
pinacol (Alfa Aesar), tetrakis(triphenylphosphine)palladium(0)
(ABCR), trimethyl borate (Fluka), triphenylphosphine (in-house
with cyclohexane. The solvent of the filtrate was evaporated and
the crude product was purified by column chromatography (silica
gel; cyclohexane/ethyl acetate, 9:1; Rf = 0.54) to obtain 2 (3.19 g,
1
chemical supply). 1-Bromo-2,7-dihydroxynaphthalene (1),[25] 2,9-di- 7.91 mmol, 74 %) as a slightly yellow solid, m.p. 26–27 °C. H NMR
chloro-1,10-phenanthroline (5),[26,27] 2,6-bis(hex-5-enyloxy)phenyl- (500 MHz, CDCl3): δ = 7.68 (d, 3J = 8.9 Hz, 1 H, 4-CnaphH), 7.65 (d,
boronic acid (6),[16] 2-[2,6-bis(hex-5-enyloxy)phenyl]-9-chloro-1,10-
phenanthroline (7),[15] 2-bromoresorcinol (9)[28,29] and 2-chloro-9-
3J = 8.9 Hz, 1 H, 5-CnaphH), 7.48 (d, J = 2.4 Hz, 1 H, 8-CnaphH), 7.07
4
3
3
4
(d, J = 8.9 Hz, 1 H, 3-CnaphH), 7.03 (dd, J = 8.9 Hz, J = 2.4 Hz, 1
3
3
3
(2,6-dimethoxyphenyl)-1,10-phenanthroline (29)[16] were synthe- H, 6-CnaphH), 5.85 (ddt, J = 17.0 Hz, J = 10.2 Hz, J = 6.6 Hz, 2 H,
3
2
4
sized according to reported procedures. Anhydrous solvents were CH=CH2), 5.05 (ddt, J = 17.0 Hz, J = 2.0 Hz, J = 1.7 Hz, 2 H, CH=
obtained with suitable desiccants. Other solvents were distilled be- CHHtrans), 4.98 (ddt, J = 10.2 Hz, J = 2.0 Hz, J = 1.2 Hz, 2 H, CH=
fore use. Column chromatography was carried out with silica gel CHHcis), 4.15 (mc, 4 H, OCH2), 2.16 (mc, 4 H, CH2CH=), 1.89 (mc, 4 H,
(Macherey–Nagel, particle size 0.04–0.063 mm). Melting points were
measured with a Gallenkamp MPD350.BM2.5 instrument or a Elec-
3
2
4
OCH2 CH2), 1.65 (m, 4 H, OCH2CH2CH2) ppm. 13C NMR (125 MHz,
CDCl3): δ = 158.8 (s, 7-Cnaph), 153.9 (s, 2-Cnaph), 138.6, 138.7 (2d,
trothermal Melting Point Apparatus. NMR spectra were recorded CH=CH2), 134.7 (s, 8a-Cnaph), 129.7 (d, 5-Cnaph), 128.4 (d, 4-Cnaph),
with a Bruker DRX 500 or Avance 600 instrument. Assignments are
supported by COSY, HSQC, and HMBC. Even when obtained by
DEPT, the type of 13C signal is always listed as singlet, doublet, etc.
125.2 (s, 4a-Cnaph), 117.5 (d, 6-Cnaph), 114.8 (t, CH=CH2), 112.3 (d, 3-
Cnaph), 108.3 (s, 1-Cnaph), 105.4 (d, 8-Cnaph), 69.9 (t, 2-Cnaph-OCH2),
67.9 (t, 7-Cnaph-OCH2), 33.4, 33.5 (2t, CH2CH=), 28.7, 28.9 (2t,
All chemical shifts are referenced to tetramethylsilane or the resid- OCH2CH2), 25.3, 25.4 (2t, OCH2CH2CH2) ppm. IR (ATR): ν = 3069
˜
ual proton or carbon of the solvent. Signal assignment in NMR spec-
(arom. C–H), 2943, 2917, 2864 (aliph. C–H), 1624, 1508 (arom. C–C),
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1261, 1213, 1072 (C–O–C), 1001, 907, 828, 787 (arom. C–H) cm–1
.
for 40 h. After cooling to room temp., dichloromethane and water
(20 mL each) were added to the solution and the layers were sepa-
rated. The aqueous layer was extracted with dichloromethane (3 ×
20 mL) and the combined organic layer was washed with half conc.
aqueous sodium chloride solution, dried with magnesium sulphate,
and the solvent was evaporated. The residue was filtered through
basic aluminium oxide with dichloromethane. After evaporation of
the solvent, the crude product was purified by column chromatog-
raphy (silica gel; dichloromethane/methanol, 98:2; Rf = 0.05) to give
8 (215 mg, 277 μmol, 65 %) as a slightly yellow solid. The product
contained isomers with migrated double bonds (see main text).
MS (EI, 70 eV): m/z (%) = 404, 402 (15, 13) [M]+·, 240, 238 (100, 98)
[M – C12H20]+·. MS (CI, isobutane): m/z (%) = 405, 403 (99, 100) [M
+ H]+. C22H27BrO2 (402.12): calcd. C 65.51, H 6.75; found C 65.69, H
6.81.
2,7-Bis(hex-5-enyloxy)naphthylboronic Acid (3): Under nitrogen,
1-bromo-2,7-bis(hex-5-enyloxy)naphthalene (2; 1.00 g, 2.48 mmol)
was dissolved in anhydrous tetrahydrofuran (16 mL) and cooled to
–78 °C. n-Butyllithium (2.5
M in hexanes, 1.10 mL, 2.75 mmol) was
added slowly and the mixture was stirred at –78 °C for 1 h. Trimethyl
borate (830 μL, 770 mg, 7.40 mmol) was then added and the mix-
ture was stirred for 2 h while warming to room temp. After the
addition of water (7 mL), the layers were separated. The aqueous
layer was extracted with diethyl ether (3 × 10 mL) and the com-
bined organic layer was washed with brine and dried with magne-
sium sulfate. The solvent was evaporated to give the crude product
3 (976 mg) as a slightly yellow, oily solid. The product could be
confirmed by mass spectra: MS (ESI, MeOH, measured as dimethyl
ester): m/z = 815 [2M + Na]+, 419 [M + Na]+. Further spectroscopic
data could not be obtained due to the instability of the product,
e.g., with NMR spectroscopy only the decomposition product 2,7-
bis(hex-5-enyloxy)naphthalene could be observed.
Method B: Under nitrogen, 7 (63.0 mg, 129 μmol), 2,7-bis(hex-5-
enyloxy)naphthylboronic acid pinacol ester (4; 70.0 mg, 155 μmol),
palladium diacetate (3.0 mg, 13 μmol), 1,3-bis(diphenylphos-
phanyl)propane (dppp, 11 mg, 26 μmol) and barium hydroxide oc-
tahydrate (63.0 mg, 200 μmol) were dissolved in 1,2-dimethoxy-
ethane (4 mL) and water (1 mL). The mixture was heated to 60 °C
for 24 h. After cooling to room temp., dichloromethane and water
(10 mL each) were added to the solution and the layers were sepa-
rated. The aqueous layer was extracted with dichloromethane (3 ×
10 mL) and the combined organic layer was washed with half conc.
aqueous sodium chloride solution, dried with magnesium sulfate
and the solvent was evaporated. The residue was filtered through
basic aluminium oxide with dichloromethane. After evaporation of
the solvent, the crude product was purified by column chromatog-
raphy (silica gel; dichloromethane/methanol, 98:2; Rf = 0.05) to give
8 (64 mg, 83 μmol, 64 %) as a slightly yellow solid. The product
contained isomers with migrated double bonds (see main text).
Pinacol 2,7-Bis(hex-5-enyloxy)naphthylboronate (4): Under
nitrogen, 1-bromo-2,7-bis(hex-5-enyloxy)naphthalene (2; 2.00 g,
4.96 mmol) was dissolved in anhydrous tetrahydrofuran (50 mL) and
cooled to –78 °C. n-Butyllithium (2.5
M in hexanes, 2.2 mL, 5.5 mmol)
was added slowly and the mixture was stirred at –78 °C for 1 h.
Trimethyl borate (700 μL, 644 mg, 6.20 mmol) was then added and
the mixture was stirred for 2 h while warming to room temp. Pin-
acol (876 mg, 7.43 mmol) was added and the reaction mixture was
heated to 60 °C for 1 h. After cooling to room temp., the suspension
was filtered through Celite before the solvent was evaporated. The
crude product was purified by column chromatography (silica gel;
cyclohexane/ethyl acetate, 19:1; Rf = 0.29) to give 4 (1.77 g,
Method C: Under nitrogen, 16 (250 mg, 560 μmol) and cesium
carbonate (2.40 g, 7.38 mmol) were dissolved in anhydrous di-
methyl sulfoxide (11 mL). After adding 6-bromo-1-hexene (980 μL,
1.19 g, 7.28 mmol) the solution was stirred at room temp. for 3 d.
The solvent was then distilled off in vacuo and the light-brown
residue was dissolved in water and dichloromethane (20 mL each),
the layers were separated and the aqueous layer was extracted with
dichloromethane (4 × 5 mL). The combined organic layer was
1
3.93 mmol, 79 %) as a yellow liquid. H NMR (500 MHz, CDCl3): δ =
7.72 (d, 3J = 8.9 Hz, 1 H, 4-CnaphH), 7.61 (d, 3J = 8.9 Hz, 1 H, 5-
washed with aqueous sodium hydroxide solution (2 M, 20 mL), dried
3
CnaphH), 7.31 (d, 4J = 2.4 Hz, 1 H, 8-CnaphH), 7.01 (d, J = 8.9 Hz, 1
with magnesium sulfate and the solvent was evaporated. The yel-
low-brown crude product was purified by column chromatography
(silica gel; dichloromethane/methanol, 98:2; Rf = 0.05) to give 8
(350 mg, 452 μmol, 81 %) as a yellow solid, m.p. 143–144 °C. 1H
3
4
H, 3-CnaphH), 6.94 (dd, J = 8.9 Hz, J = 2.4 Hz, 1 H, 6-CnaphH), 5.84
3
3
3
(ddt, J = 17.0 Hz, J = 10.2 Hz, J = 6.6 Hz, 2 H, CH=CH2), 5.04 (mc,
2 H, CH=CHHtrans), 4.97 (mc, 2 H, CH=CHHcis), 4.06 (mc, 4 H, OCH2),
2.13 (mc, 4 H, CH2CH=), 1.84 (mc, 4 H, OCH2CH2), 1.61 (mc, 4 H,
OCH2CH2CH2), 1.46 (s, 12 H, CH3) ppm. 13C NMR (125 MHz, CDCl3):
δ = 161.9 (s, 2-Cnaph), 157.6 (s, 7-Cnaph), 138.8 (s, 8a-Cnaph), 138.60,
138.62 (2d, CH=CH2), 131.4 (d, 4-Cnaph), 129.5 (d, 5-Cnaph), 124.3 (s,
4a-Cnaph), 116.4 (d, 6-Cnaph), 114.65, 114.74 (2t, CH=CH2), 111.1 (d,
3-Cnaph), 105.9 (d, 8-Cnaph), 83.7 [s, OC(CH3)2], 68.8 (t, 2-Cnaph-OCH2),
67.5 (t, 7-Cnaph-OCH2), 33.5, 33.6 (2t, CH2CH=), 28.7, 29.2 (2t,
OCH2CH), 25.41, 25.49 (2t, OCH2CH2CH2), 25.0 (q, CH3) ppm. IR (ATR):
3
NMR (500 MHz, CDCl3): δ = 8.31 (d, J = 8.2 Hz, 1 H, 4-CphenH), 8.23
3
3
(d, J = 8.2 Hz, 1 H, 7-CphenH), 7.87 (s, 2 H, 5,6-CphenH), 7.78 (d, J =
3
9.0 Hz, 1 H, 4-CnaphH), 7.73 (d, J = 8.2 Hz, 1 H, 3-CphenH), 7.68 (d,
3J = 8.9 Hz, 1 H, 5-CnaphH), 7.65 (d, J = 8.2 Hz, 1 H, 8-CphenH), 7.21
3
3
3
(t, J = 8.4 Hz, 1 H, 4-CarH), 7.16 (d, J = 9.0 Hz, 1 H, 3-CnaphH), 6.95
3
4
4
(dd, J = 8.9 Hz, J = 2.4 Hz, 1 H, 6-CnaphH), 6.91 (d, J = 2.4 Hz, 1
H, 8-CnaphH), 6.59 (d, 3J = 8.4 Hz, 2 H, 3,5-CarH), 5.68 [ddt, 3J =
17.1 Hz, 3J = 10.2 Hz, 3J = 6.7 Hz, 1 H, 7-CnaphO(CH2)4CH=], 5.59–
5.47 [m, 3 H, 2-CnaphO(CH2)4CH=, CarO(CH2)4CH=], 4.90 [ddt, 3J =
17.1 Hz, 2J = 2.0 Hz, 4J = 1.6 Hz, 1 H, 7-CnaphO(CH2)4CH=CHHtrans],
ν = 3076 (arom. C–H), 2976, 2932, 2866 (aliph. C–H), 1622, 1509
˜
(arom. C–C), 1445 (aliph. C–H), 1236, 1211, 1142, 1070 (C–O–C), 994,
907, 849, 826 (arom. C–H) cm–1. MS (EI, 70 eV): m/z (%) = 450 (100)
[M]+·, 368 (10) [M – C6H10]+·, 324 [M – C6H12BO2]+·. MS (CI, isobu-
tane): m/z (%) = 451 (100) [M + H]+. C28H39BO4 (450.29): calcd. C
74.66, H 8.73; found C 74.82, H 9.12.
4.86 [ddt, 3J = 10.2 Hz, 2J = 2.0 Hz, 4J = 1.2 Hz, 1 H, 7-Cnaph
-
O(CH2)4CH=CHHcis], 4.81–4.73 [m, 6 H, 2-CnaphO(CH2)3CH=CH2,
3
CarO(CH2)3CH=CH2], 4.02 (t, J = 6.4 Hz, 2 H, 2-CnaphOCH2), 3.89 (t,
3J = 6.5 Hz, 4 H, CarOCH2), 3.70 (t, 3J = 6.4 Hz, 2 H, 7-CnaphOCH2),
2-[2,7-Bis(hex-5-enyloxy)naphthyl]-9-[2,6-bis(hex-5-enyloxy)-
phenyl]-1,10-phenanthroline (8). Method A: Under nitrogen, 2-
[2,6-bis(hex-5-enyloxy)phenyl]-9-chloro-1,10-phenanthroline (7;
208 mg, 427 μmol), the crude product of 2,7-bis(hex-5-enyl-
oxy)naphthylboronic acid (3; 303 mg, ≤ 770 μmol), tetrakis(triphen-
ylphosphine)palladium(0) (47 mg, 41 μmol) and barium hydroxide
1.93 [tdt, 3J = 7.4 Hz, 3J = 6.7 Hz, 4J = 1.3 Hz, 2 H, 7-Cnaph
-
O(CH2)3CH2], 1.86–1.80 [m, 2 H, 2-CnaphO(CH2)3CH2], 1.80–1.73 [m, 4
H, CarO(CH2)3CH2], 1.60–1.50 (m, 4 H, CnaphOCH2CH2), 1.50–1.43 (m,
4 H, CarOCH2CH2), 1.39–1.31 [m, 2 H, 7-CnaphO(CH2)2CH2], 1.28–1.20
[m, 2 H, 2-CnaphO(CH2)2CH2], 1.20–1.13 [m, 4 H, CarO(CH2)2CH2] ppm.
13C NMR (125 MHz, CDCl3): δ = 158.1 (s, 2,6-Car), 157.8 (s, 7-Cnaph),
octahydrate (201 mg, 637 μmol) were dissolved in 1,2-dimethoxy- 157.0 (s, 2-Cphen), 155.4 (s, 9-Cphen), 155.0 (s, 2-Cnaph), 146.7 (s, 10b-
ethane (12 mL) and water (3 mL). The mixture was heated to 80 °C Cphen), 146.3 (s, 10a-CPhen), 138.8, 138.7 (2d, CH=CH2), 135.6 (d, 4-
Eur. J. Org. Chem. 2016, 1119–1131
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CPhen), 135.0 (s, 8a-Cnaph), 134.9 (d, 7-Cphen), 129.9 (d, 4-Cnaph), 129.7
(d, 4-Car), 129.4 (d, 5-Cnaph), 127.54 (s, 6a-Cphen), 127.48 (s, 4a-Cphen),
126.6 (d, 6-Cphen), 126.5 (d, 8-Cphen*), 126.4 (d, 3-Cphen*), 126.1 (d,
5-Cphen), 124.9 (s, 4a-Cnaph), 124.7 (s, 1-Cnaph), 121.6 (s, 1-Car), 116.5
(d, 6-Cn a ph ), 114.6 [t, 7-Cn a p hO(CH2 )4 CH=CH2 ], 114.3 [t,
2-CnaphO(CH2)4CH=CH2], 114.2 [t, CarO(CH2)4CH=CH2], 112.8 (d, 3-
Cnaph), 106.6 (d, 3,5-Car), 105.0 (d, 8-Cnaph), 69.7 (t, 2-CnaphOCH2),
69.3 (t, CarOCH2), 67.6 (t, 7-CnaphOCH2), 33.6 [t, 7-CnaphO(CH2)3CH2],
33.3 [t, 2-CnaphO(CH2)3CH2], 33.2 [t, CarO(CH2)3CH2], 28.9 (t,
2-CnaphOCH2CH2), 28.7 (t, 7-CnaphOCH2CH2), 28.5 (t, CarOCH2CH2),
25.4 [t, 7-CnaphO(CH2)2CH2], 25.2 [t, 2-CnaphO(CH2)2CH2], 25.1 [t,
dimethyl ester): m/z = 385 [M + Na]+. C20H19BO4 (334.14): calcd. C
71.88, H 5.73; found C 71.81, H 5.81.
2,7-Bis(benzyloxy)-1-bromonaphthalene (12): Under nitrogen, 1-
bromo-2,7-dihydroxynaphthalene (1; 7.00 g, 29.3 mmol) and anhy-
drous potassium carbonate (9.70 g, 70.3 mmol) were suspended in
anhydrous acetone (80 mL) and heated to 60 °C for 1 h. After addi-
tion of benzyl bromide (8.40 mL, 12.0 g, 70.3 mmol), the black mix-
ture was heated to 60 °C for 2 h. After cooling, dichloromethane
(120 mL) was added and the salt was filtered off. The solvent was
evaporated and the black, oily residue was recrystallized first from
n-hexane/dichloromethane (6:1) and then from n-hexane/dichloro-
methane (4:1). The still black crude product was purified by column
chromatography (silica gel; cyclohexane/ethyl acetate, 19:1; Rf =
0.27) to give 12 (8.80 g, 21.0 mmol, 72 %) as a slightly yellow solid,
m.p. 103 °C. 1H NMR (500 MHz, CDCl3): δ = 7.67 (d, 3J = 8.8 Hz, 1
H, 4-CnaphH), 7.66 (d, 3J = 8.9 Hz, 1 H, 5-CnaphH), 7.63 (d, 4J = 2.4 Hz,
1 H, 8-CnaphH), 7.54–7.50 (m, 4 H, 2,6-CbnH), 7.43–7.37 (m, 4 H, 3,5-
CarO(CH2)2CH2] ppm. * Assignment may be reversed. IR (ATR): ν =
˜
3074 (arom. C–H), 2936, 2862 (aliph. C–H), 1622, 1588 (arom. C–C),
1455 (aliph. C–H), 1237, 1223, 1209, 1090, 1070 (C–O–C), 992, 906,
856, 826 (arom. C–H) cm–1. MS (ESI, CHCl3/MeOH): m/z = 797 [M +
Na]+, 775 [M + H]+. C52H58N2O4 (744.44): calcd. C 80.59, H 7.54, N
3.61; found C 80.51, H 7.75, N 3.70.
3
4
1,3-Bis(benzyloxy)-2-bromobenzene (10): Under nitrogen, 2-
CbnH), 7.37–7.30 (m, 2 H, 4-CbnH), 7.11 (dd, J = 8.9 Hz, J = 2.4 Hz,
bromoresorcinol (9; 10.0 g, 52.9 mmol) and anhydrous potassium 1 H, 6-CnaphH), 7.11 (d, 3J = 8.8 Hz, 1 H, 3-CnaphH), 5.28 (s, 2 H, 2-
carbonate (16.1 g, 116 mmol) were suspended in anhydrous acet-
one (120 mL). After addition of benzyl bromide (14.0 mL, 20.2 g,
118 mmol), the mixture was heated to reflux for 6.5 h. After cooling,
dichloromethane (100 mL) was added and the salt was filtered off
and washed with additional dichloromethane (150 mL). The solvent
was evaporated and the residue was recrystallized from cyclohex-
CnaphOCH2), 5.23 (s, 2 H, 7-CnaphOCH2) ppm. 13C NMR (125 MHz,
CDCl3): δ = 158.6 (s, 7-Cnaph), 153.7 (s, 2-Cnaph), 136.9, 136.8 (2s, 1-
Cbn), 134.8 (s, 8a-Cnaph), 129.9 (d, 5-Cnaph), 128.8, 128.7 (2d, 3,5-Cbn),
128.6 (d, 4-Cnaph), 128.3, 128.1 (2d, 4-Cbn), 128.0 (d, 7-CnaphOCH2-
2,6-Cbn), 127.3 (d, 2-CnaphOCH2-2,6-Cbn), 125.7 (s, 4a-Cnaph), 117.9 (d,
6-Cnaph), 113.0 (d, 3-Cnaph), 109.0 (s, 1-Cnaph), 106.2 (d, 8-Cnaph), 71.8
ane (70 mL) to give 10 (17.9 g, 48.5 mmol, 92 %) as a white solid, (t, 2-CnaphOCH2), 70.3 (t, 7-CnaphOCH2) ppm. IR (ATR): ν = 3063, 3031
˜
m.p. 96–97 °C. 1H NMR (500 MHz, CDCl3): δ = 7.50–7.46 (m, 4 H, (arom. C–H), 2871 (aliph. C–H), 1626, 1603, 1509 (arom. C–C), 1453,
2,6-CbnH), 7.40–7.36 (m, 4 H, 3,5-CbnH), 7.33–7.29 (m, 2 H, 4-CbnH),
1379, 1346 (aliph. C–H), 1264, 1244, 1220, 1202, 1004 (C–O–C), 818,
727, 719, 692 (arom. C–H) cm–1. MS (EI, 70 eV): m/z (%) = 420, 418
(100, 91) [M]+·, 339 (34) [M – Br]+. MS (CI, isobutane): m/z (%) = 421,
3
3
7.14 (t, J = 8.3 Hz, 1 H, 4-CarH), 6.60 (d, J = 8.3 Hz, 2 H, 3,5-CarH),
5.16 (s, 4 H, OCH2) ppm. 13C NMR (125 MHz, CDCl3): δ = 156.6 (s,
2,6-Car), 136.8 (s, 1-Cbn), 128.7 (d, 3,5-Cbn), 128.2 (d, 4-Car), 128.0 (d, 419 (100, 94) [M + H]+. C24H19BrO2 (418.06): calcd. C 68.75, H 4.57;
4-Cbn), 127.1 (d, 2,6-Cbn), 106.9 (d, 3,5-Car), 102.9 (s, 1-Car), 71.1 (t,
found C 68.69, H 4.55.
OCH2) ppm. IR (ATR): ν = 3065, 3032 (arom. C–H), 2907, 2862 (aliph.
˜
Pinacol 2,7-Bis(benzyloxy)naphthylboronate (13): Under nitro-
gen, 2,7-bis(benzyloxy)-1-bromonaphthalene (12; 2.00 g,
4.77 mmol) was dissolved in anhydrous tetrahydrofuran (90 mL) and
C–H), 1606, 1593, 1571 (arom. C–C), 1474, 1449 (aliph. C–H), 1257
(C–O–C), 1035 (C–Br), 760, 727, 692 (arom. C–H) cm–1. MS (EI, 70 eV):
m/z (%) = 370, 368 (14, 16) [M]+·, 289 (3) [M – Br]+, 181 (100) [M –
C7H8BrO]+. MS (CI, isobutane): m/z (%) = 371, 369 (100, 99) [M +
H]+. C20H17BrO2 (368.04): calcd. C 65.05, H 4.64; found C 65.26, H
4.62.
cooled to –78 °C. n-Butyllithium (2.5
M in hexanes, 2.00 mL,
5.01 mmol) was added and the mixture was stirred at –78 °C for
1 h. Isopropoxyboronic acid pinacol ester (1.95 mL, 1.78 g,
9.54 mmol) was added and the mixture was stirred for 1.5 h while
warming to room temp., followed by heating the mixture to 60 °C
for 2.5 h. After cooling to room temp., water and diethyl ether
(50 mL each) were added to the suspension and the layers were
separated. The aqueous layer was extracted with diethyl ether (3 ×
30 mL) and the combined organic layer was washed with brine and
dried with magnesium sulfate. The solvent was evaporated and the
orange-brown residue was purified by column chromatography (sil-
ica gel; cyclohexane/ethyl acetate, 14:1; Rf = 0.19) to give 13 (1.13 g,
2,6-Bis(benzyloxy)phenylboronic Acid (11): Under nitrogen, 1,3-
bis(benzyloxy)-2-bromobenzene (10; 10.0 g, 27.1 mmol) was dis-
solved in anhydrous tetrahydrofuran (65 mL) and cooled to –78 °C.
Slowly, n-butyllithium (2.5
M in hexanes, 11.9 mL, 29.8 mmol) was
added over a period of 1 h and the mixture was stirred at –78 °C
for another 40 min. Trimethyl borate (6.0 mL, 5.6 g, 54 mmol) was
then added and the mixture was stirred for 16 h while warming to
room temp. After the addition of water and diethyl ether (50 mL
each), the layers were separated. The aqueous layer was extracted
with diethyl ether (3 × 30 mL) and the combined organic layer was
washed with brine (30 mL) and dried with magnesium sulfate. Ap-
1
2.42 mmol, 51 %) as a white solid, m.p. 112 °C. H NMR (500 MHz,
3
3
CDCl3): δ = 7.76 (d, J = 8.9 Hz, 1 H, 4-CnaphH), 7.66 (d, J = 8.9 Hz,
1 H, 5-CnaphH), 7.55–7.52 (m, 2 H, 2-CnaphOCH2-2,6-CbnH), 7.51–7.46
proximately 25 g of silica gel was added, and the solvent was evap- (m, 3 H, 8-CnaphH, 7-CnaphOCH2-2,6-CbnH), 7.43–7.29 (m, 6 H, 3,4,5-
4
orated in vacuo. The resulting product was loaded on silica gel and
transferred to the top of a silica gel filled column. Subsequent col-
umn chromatography (silica gel; cyclohexane/ethyl acetate, 3:1; Rf =
CbnH), 7.11 (d, 3J = 8.9 Hz, 1 H, 3-CnaphH), 7.07 (dd, 3J = 8.9 Hz, J =
2.5 Hz, 1 H, 6-CnaphH), 5.20 (s, 2 H, 2-CnaphOCH2), 5.17 (s, 2 H, 7-
CnaphOCH2), 1.38 (s, 12 H, CH3) ppm. 13C NMR (125 MHz, CDCl3): δ =
0.30) gave 11 (4.91 g, 14.7 mmol, 54 %) as a yellow solid, m.p. 161.7 (s, 2-Cnaph), 157.5 (7-Cnaph), 138.8 (s, 8a-Cnaph), 137.5 (s, 2-
1
127 °C. H NMR (500 MHz, CDCl3): δ = 7.44–7.33 (m, 11 H, CbnH, 4-
Cnaph-OCH2-1-Cbn), 137.0 (s, 7-Cnaph-OCH2-1-Cbn), 131.6 (d, 4-Cnaph),
CArH), 7.20 (s, 2 H, OH), 6.71 (d, J = 8.4 Hz, 2 H, 3,5-CarH), 5.14 (s, 4 129.6 (d, 5-Cnaph), 128.6 (d, 2-Cnaph-OCH2-3,5-Cbn*1), 128.2 (d, 7-
3
H, OCH3) ppm. 13C NMR (125 MHz, CDCl3): δ = 164.9 (s, 2,6-Car),
Cnaph-OCH2-3,5-Cbn*1), 127.9 (d, 2-Cnaph-OCH2-4-Cbn*2), 127.64 (d, 7-
Cnaph-OCH2-4-Cbn*2), 127.57 (d, 2,6-Cbn), 124.8 (s, 4a-Cnaph), 116.7 (d,
6-Cnaph), 111.8 (d, 3-Cnaph), 106.6 (d, 8-Cnaph), 83.7 [s, OC(CH3)2], 71.2
135.7 (s, 1-Cbn), 133.1 (d, 4-Car), 129.1 (d, 3,5-Cbn), 128.8 (d, 4-Cbn),
127.9 (d, 2,6-Cbn), 106.1 (d, 3,5-C ), 71.4 (t, OCH ) ppm. IR (ATR): ν =
˜
ar
2
3499 (OH), 3030 (arom. C–H), 2954, 2889 (aliph. C–H), 1590, 1574 (t, 2-Cnaph-OCH2), 69.8 (t, 7-Cnaph-OCH2), 25.0 (q, CH3) ppm. *1,*2
(arom. C–C), 1474, 1454, 1317 (aliph. C–H), 1233, 1091, 1058 (C–O–
Assignments may be reversed, respectively. IR (ATR): ν = 3068 (arom.
C–H), 2974, 2908, 2863 (aliph. C–H), 1621, 1595, 1575, 1511 (arom.
˜
C), 789, 744, 692 (arom. C–H) cm–1. MS (ESI, MeOH, measured as
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C–C), 1434, 1372, 1334, 1311 (aliph. C–H), 1238, 1207, 1139, 1064
(C–O–C), 1006, 833, 760, 734, 699 (arom. C–H) cm–1. MS (EI, 70 eV):
CbnH, 7-CnaphOCH2-CbnH), 6.85 (d, 4J = 2.3 Hz, 1 H, 8-CnaphH), 6.77
(d, 3J = 8.5 Hz, 2 H, 3,5-CarH), 5.12 (s, 2 H, 2-CnaphOCH2), 4.97 (s, 4
m/z (%) = 466 (100) [M]+·. MS (CI, isobutane): m/z (%) = 467 (100) H, CarOCH2), 4.72 (s, 2 H, 7-CnaphOCH2) ppm. 13C NMR (151 MHz,
[M + H]+. C30H31BO4 (466.23): calcd. C 77.26, H 6.70; found C 77.45,
H 6.75.
[D6]DMSO): δ = 156.8 (s, 7-Cnaph), 156.7 (s, 2,6-Car), 156.0 (s, 2-Cphen),
154.8 (s, 9-Cphen), 153.9 (s, 2-Cnaph), 145.8 (s, 10b-Cphen), 145.6 (s,
10a-Cphen), 137.2 (s, 2-CnaphOCH2-1-Cbn), 137.1 (s, CArOCH2-1-Cbn),
136.5 (s, 7-CnaphOCH2-1-Cbn), 136.1 (d, 4-Cphen), 135.6 (d, 7-Cphen),
134.0 (s, 8a-Cnaph), 129.7 (d, 4-Cnaph), 129.64 (d, 4-Car), 129.60 (d, 5-
Cnaph), 128.1 (d, 2-CnaphOCH2-3,5-Cbn), 127.98 (d, 7-CnaphOCH2-3,5-
2-[2,6-Bis(benzyloxy)phenyl]-9-chloro-1,10-phenanthroline
(14): Under nitrogen, 2,9-dichloro-1,10-phenanthroline (5; 884 mg,
3.55 mmol), 2,6-bis(benzyloxy)phenylboronic acid (11; 1.30 g,
3.89 mmol), tetrakis(triphenylphosphine)palladium(0) (415 mg,
359 μmol) and sodium carbonate (1.13 g, 10.7 mmol) were dis-
solved in 1,2-dimethoxyethane (72 mL) and water (18 mL). The mix-
ture was heated to 80 °C for 19 h. After cooling to room temp.,
dichloromethane and water were added and the layers were sepa-
rated. The aqueous layer was extracted with dichloromethane three
times, and the combined organic layer was washed with brine,
dried with magnesium sulfate and the solvent was evaporated. The
residue was filtered through basic aluminium oxide with dichloro-
methane. After evaporation of the solvent, the crude product was
purified by column chromatography (silica gel; dichloromethane/
methanol, 199:1; Rf = 0.11) to give 14 (1.05 g, 2.09 mmol, 59 %) as
C
bn), 127.96 (d, CarOCH2-3,5-Cbn), 127.4 (d, 7-CnaphOCH2-4-Cbn),
127.29 (br. d, 2-CnaphOCH2-4-Cbn, 7-CnaphOCH2-2,6-Cbn), 127.23 (s,
6a-Cphen), 127.17 (s, 4a-Cphen), 127.10 (d, CarOCH2-4-Cbn), 127.07 (d,
2-CnaphOCH2-2,6-Cbn), 126.8 (d, CarOCH2-2,6-Cbn), 126.5 (d, 6-Cphen),
126.3 (d, 5-Cphen), 126.0 (d, 3-Cphen*), 125.8 (d, 8-Cphen*), 124.3 (s,
4a-Cnaph), 123.8 (s, 1-Cnaph), 120.5 (s, 1-Car), 116.1 (d, 6-Cnaph), 112.8
(d, 3-Cnaph), 106.2 (d, 3,5-Car), 105.2 (d, 8-Cnaph), 70.0 (t, 2-Cnaph
-
OCH2), 69.4 (t, CarOCH2), 69.2 (t, 7-CnaphOCH2) ppm. * Assignment
may be reversed. IR (ATR): ν = 3031 (arom. C–H), 2862 (aliph. C–H),
˜
1621, 1591 (arom. C–C), 1510, 1496, 1447 (aliph. C–H), 1249, 1111
(C–O–C), 851, 826, 730, 694 (arom. C–H) cm–1. MS (EI, 70 eV): m/z
(%) = 806 (80) [M]+·, 715 (100) [M – C7H7]+, 533 (33) [M – C21H21]+.
MS (CI, isobutane): m/z (%) = 807 (52) [M + H]+. MS (ESI, CHCl3/
MeOH): m/z = 807 [M + H]+. C56H42N2O4 (806.31): calcd. C 83.35, H
5.25, N 3.47; found C 83.64, H 5.20, N 3.42.
1
a yellow solid, m.p. 169 °C. H NMR (600 MHz, CDCl3): δ = 8.19 (d,
3
3J = 8.4 Hz, 1 H, 7-CphenH), 8.18 (d, J = 8.2 Hz, 1 H, 4-CphenH), 7.81
(d, 3J = 8.2 Hz, 1 H, 3-CphenH), 7.80 (d, 3J = 8.7 Hz, 1 H, 5-CphenH),
7.74 (d, 3J = 8.7 Hz, 1 H, 6-CphenH), 7.62 (d, 3J = 8.4 Hz, 1 H, 8-
CphenH), 7.42–7.38 (m, 4 H, 2,6-CbnH), 7.32 (t, 3J = 8.4 Hz, 1 H, 4- 2-(2,7-Dihydroxynaphthyl)-9-(2,6-dihydroxyphenyl)-1,10-phen-
CarH), 7.18–7.13 (m, 6 H, 3,4,5-CbnH), 6.77 (d, 3J = 8.4 Hz, 2 H, 3,5-
anthroline (16): In ethyl acetate (45 mL), most of 15 (601 mg,
CarH), 5.13 (s, 4 H, OCH2) ppm. 13C NMR (151 MHz, CDCl3): δ = 158.0 745 μmol) was dissolved by heating. Nitrogen was then bubbled
(s, 2,6-Car), 155.5 (s, 2-Cphen), 151.1 (s, 9-Cphen), 146.6 (s, 10a-Cphen), through the solution for 10 min while cooling to room temp. Pearl-
145.0 (s, 10b-Cphen), 138.7 (d, 7-Cphen), 137.5 (s, 1-Cbn), 135.0 (d, 4- man's catalyst [20 % Pd(OH)2 on charcoal (50 % water), 205 mg,
Cphen), 130.3 (d, 4-Car), 128.3, 127.9, 127.51, 127.46, 127.29, 127.25
(s, 5d, 3,4a,6a,5-Cphen, 2,3,4,5,6-Cbn), 125.3 (d, 6-Cphen), 123.9 (d, 8-
146 μmol] and palladium on charcoal (10 %, 146 mg, 149 μmol)
were added and nitrogen was bubbled through the suspension for
another 10 min. Hydrogen was then bubbled through the suspen-
Cphen), 121.1 (s, 1-Car), 106.9 (d, 3,5-Car), 71.1 (t, OCH2) ppm. IR (ATR):
ν = 3027 (arom. C–H), 2869 (aliph. C–H), 1580 (arom. C–C), 1480, sion for 2 h. The suspension was stirred under hydrogen for 20 h,
˜
1450 (aliph. C–H), 1247, 1100, 1075 (C–O–C), 891, 848, 743, 697
(arom. C–H) cm–1. MS (EI, 70 eV): m/z (%) = 502 (74) [M]+·, 395 (88)
[M – C7H7O]+, 290 (100) [M – C14H14O2]+·. MS (CI, isobutane): m/z
then the catalyst was removed by centrifugation, and the catalyst
was heated again with hot ethyl acetate/methanol (1:1, 6 × 20 mL),
followed by additional centrifugation. The solvent of the combined
(%) = 503 (100) [M + H]+. C32H23ClN2O2 (502.14): calcd. C 76.41, H organic layer was evaporated to give 16 (311 mg, 697 μmol, 94 %)
4.61, N 5.57; found C 76.21, H 4.73, N 5.53.
as an orange-red solid, m.p. 230 °C (decomposition). 1H NMR
(600 MHz, [D6]DMSO): δ = 13.21 (s, 2 H, CarOH), 10.12 (s, 1 H, 2-
CnaphOH), 9.36 (s, 1 H, 7-CnaphOH), 9.03 (d, 3J = 8.9 Hz, 1 H, 8-CphenH),
8.67 (d, 3J = 8.9 Hz, 1 H, 7-CphenH), 8.64 (d, 3J = 8.3 Hz, 1 H, 4-
2-[2,7-Bis(benzyloxy)naphthyl]-9-[2,6-bis(benzyloxy)phenyl]-
1,10-phenanthroline (15): Under nitrogen, 14 (270 mg, 536 μmol),
2,7-bis(benzyloxy)naphthylboronic acid pinacol ester (13; 375 mg,
804 μmol), [1,1′-bis(diphenylphosphanyl)ferrocene]dichloropalla-
dium(II) (60 mg, 73 μmol) and barium hydroxide octahydrate
(470 mg, 149 mmol) were dissolved in 1,2-dimethoxyethane (32 mL)
and water (8 mL). The mixture was heated to 70 °C for 20 h. After
cooling to room temp., dichloromethane and water (50 mL each)
were added to the dark-green solution and the layers were sepa-
rated. The aqueous layer was extracted with dichloromethane (5 ×
50 mL) and the combined organic layer was washed with half conc.
aqueous sodium chloride solution, dried with magnesium sulfate
and the solvent was evaporated. The dark-green residue was filtered
through basic aluminium oxide with dichloromethane. After evapo-
ration of the solvent, the yellow crude product was purified by col-
umn chromatography (silica gel; dichloromethane/methanol, 98:2;
Rf = 0.15) to give 15 (246 mg, 305 μmol, 57 %) as a slightly yellow
3
3
CphenH), 8.12 (d, J = 8.8 Hz, 1 H, 5-CphenH), 8.09 (d, J = 8.8 Hz, 1
H, 6-CphenH), 7.88 (d, 3J = 8.2 Hz, 1 H, 3-CphenH), 7.79 (d, 3J = 8.8 Hz,
1 H, 4-CnaphH), 7.73 (d, 3J = 8.8 Hz, 1 H, 5-CnaphH), 7.11 (d, 3J =
8.8 Hz, 1 H, 3-CnaphH), 7.07 (t, 3J = 8.1 Hz, 1 H, 4-CarH), 6.86 (dd, 3J =
8.8 Hz, 4J = 2.1 Hz, 1 H, 6-CnaphH), 6.76 (d, 4J = 2.1 Hz, 1 H, 8-
CnaphH), 6.40 (d, 3J = 8.1 Hz, 2 H, 3,5-CarH) ppm. 13C NMR (151 MHz,
[D6]DMSO): δ = 159.9 (s, 2,6-Car), 157.5 (s, 2-Cphen), 156.4 (s, 9-Cphen),
156.1 (s, 7-Cnaph), 153.3 (s, 2-Cnaph), 143.5 (s, 10b-Cphen), 141.3 (s,
10a-Cphen), 137.4 (d, 7-Cphen), 136.7 (d, 4-Cphen), 134.7 (s, 8a-Cnaph),
131.4 (d, 4-Car), 130.0 (d, 4-Cnaph), 129.7 (d, 5-Cnaph), 127.2 (s, 4a-
Cphen), 127.0 (d, 3-Cphen), 126.3 (d, 5-Cphen), 126.2 (s, 6a-Cphen), 125.7
(d, 6-Cphen), 124.5 (d, 8-Cphen), 122.8 (s, 4a-Cnaph), 118.7 (s, 1-Cnaph),
115.3 (d, 6-Cnaph), 115.1 (d, 3-Cnaph), 107.9 (s, 1-Car), 107.5 (d, 3,5-
Car), 105.6 (d, 8-Cnaph) ppm. IR (ATR): ν = 3307 (O–H), 1621, 1604,
˜
1576 (arom. C-C), 1496, 1470 (O-H), 1348, 1227, 1197 (arom.), 852,
787, 734 (arom. C-H) cm–1. MS (MALDI, Cl-CCA): m/z = 447 [M + H]+.
C28H18N2O4 (446.13): calcd. C 75.33, H 4.06, N 6.27; found C 74.84,
H 4.30, N 5.92.
1
3
solid, m.p. 188 °C. H NMR (600 MHz, [D6]DMSO): δ = 8.57 (d, J =
3
8.2 Hz, 1 H, 4-CphenH), 8.53 (d, J = 8.2 Hz, 1 H, 7-CphenH), 8.09 (mc,
2 H, 5,6-CphenH), 7.94 (d, 3J = 9.1 Hz, 1 H, 4-CnaphH), 7.84 (d, 3J =
9.0 Hz, 1 H, 5-CnaphH), 7.755 (d, 3J = 8.2 Hz, 1 H, 8-CphenH), 7.750 (d,
3J = 8.2 Hz, 1 H, 3-CphenH), 7.41 (d, J = 9.1 Hz, 1 H, 3-CnaphH), 7.28
2-[2,7-Bis(pent-4-enyloxy)naphthyl]-9-[2,6-bis(pent-4-enyl-
3
(t, 3J = 8.5 Hz, 1 H, 4-CarH), 7.28–7.26 (m, 2 H, 2-CnaphOCH2-2,6- oxy)phenyl]-1,10-phenanthroline (17): Under nitrogen, 16
CbnH), 7.20–7.17 (m, 4 H, CarOCH2-2,6-CbnH), 7.09–7.04 (m, 4 H, 6-
(401 mg, 889 μmol) and cesium carbonate (3.80 g, 11.7 mmol) were
CnaphH, 2-CnaphOCH2-3,4,5-CbnH), 7.04–6.91 (m, 11 H, CarOCH2-3,4,5-
dissolved in anhydrous dimethyl sulfoxide (18 mL). After adding 5-
Eur. J. Org. Chem. 2016, 1119–1131
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bromo-1-pentene (1.40 mL, 1.74 g, 11.7 mmol), the solution was laps of the four diastereomers generated by ring closing metathesis,
stirred at room temp. for 4 d, then the solvent was distilled off in
vacuo. The light-brown residue was dissolved in water and dichloro-
methane (50 mL each), the layers were separated and the aqueous
layer was extracted with dichloromethane (3 × 20 mL). The com-
bined organic layer was washed with aqueous sodium hydroxide
complete determination of the signals was not possible. IR (ATR):
ν = 2929, 2864 (aliph. C–H), 1621, 1585 (arom. C–C), 1510, 1494,
˜
1455 (aliph. C–H), 1227, 1208, 1096 (C–O–C), 968, 855, 827, 720
(arom. C–C) cm–1. MS (ESI, CHCl3/MeOH): m/z = 685 [M + Na]+, 663
[M + H]+. MS (MALDI, Cl-CCA): m/z = 663, [M + H]+. HRMS (FT-ICR):
m/z calcd. For C44H43N2O4 [M + H]+: 663.321; found: 663.322 (Δ =
+
solution (2
M, 20 mL), dried with magnesium sulfate, and the solvent
was evaporated. The orange-brown crude product was purified by
column chromatography (silica gel; dichloromethane/methanol,
98:2; Rf = 0.07) to give 17 (521 mg, 725 μmol, 81 %) as a yellow
2 ppm).
2,13,15,26-Tetraoxa-1(1,3,2)-benzena-14(2,7,1)-naphthalina-
27(2,9)-1,10-phenanthrolina-bicyclo[12.12.1]heptacosaphane-
7,20-diene (rac-18c): Under nitrogen, 8 (338 mg, 436 μmol) and
benzylidene-bis(tricyclohexylphosphine)dichlororuthenium (Grubbs
type I catalyst, 36 mg, 44 μmol) were dissolved in anhydrous di-
chloromethane (440 mL). The solution was stirred at room temp.
for 18 h, then ethyl vinyl ether (20 mL) was added and the mixture
was stirred at room temp. for 1 h. The mixture was filtered through
basic aluminium oxide (dichloromethane) before the solvent was
evaporated. The beige crude product was purified by column chro-
matography (silica gel; dichloromethane/methanol, 98:2; Rf = 0.19–
0.04) to give rac-18c (263 mg, 366 μmol, 84 %) as a light-yellow
solid, m.p. 247–249 °C. NMR spectra were measured (see the Sup-
porting Information); however, due to signal overlaps of the four
diastereomers generated by ring closing metathesis, complete de-
1
solid, m.p. 151–153 °C. H NMR (500 MHz, [D6]DMSO): δ = 8.58 (d,
3
3J = 8.2 Hz, 1 H, 4-CphenH), 8.48 (d, J = 8.3 Hz, 1 H, 7-CphenH), 8.08
3
3
(d, J = 8.8 Hz, 1 H, 5-CphenH*), 8.06 (d, J = 8.8 Hz, 1 H, 6-CphenH*),
7.94 (d, 3J = 9.0 Hz, 1 H, 4-CnaphH), 7.84 (d, 3J = 9.0 Hz, 1 H, 5-
CnaphH), 7.76 (d, 3J = 8.2 Hz, 1 H, 3-CphenH), 7.60 (d, J = 8.3 Hz, 1
3
H, 8-CphenH), 7.35 (d, 3J = 9.0 Hz, 1 H, 3-CnaphH), 7.28 (t, 3J = 8.4 Hz,
3
4
1 H, 4-CarH), 7.01 (dd, J = 9.0 Hz, J = 2.5 Hz, 1 H, 6-CnaphH), 6.69
(d, 3J = 8.4 Hz, 2 H, 3,5-CarH), 6.69 (d, 4J = 2.5 Hz, 1 H, 8-CnaphH),
5.61–5.51 [m, 2 H, CnaphO(CH2)3CH=], 5.47 [ddt, 3J = 18.2 Hz, 3J =
9.2 Hz, 3J = 6.6 Hz, 2 H, CarO(CH2)3CH=], 4.78 [ddt, 3J = 17.2 Hz, 2J =
4
2.0 Hz, J = 1.6 Hz, 1 H, 7-CnaphO(CH2)3CH=CHHtrans], 4.76–4.70 [m,
3 H, 7-CnaphO(CH2)3CH=CHHcis, 2-CnaphO(CH2)3CH=CH2], 4.66–4.60
3
[m, 4 H, CarO(CH2)3CH=CH2], 4.03 (t, J = 6.3 Hz, 2 H, 2-CnaphOCH2),
3.84 (t, 3J = 6.3 Hz, 4 H, CarOCH2), 3.64 (t, 3J = 6.4 Hz, 2 H, 7-
CnaphOCH2), 1.90 [mc, 2 H, 7-CnaphO(CH2)2CH2], 1.83 [mc, 2 H, 2-
termination of the signals was not possible. IR (ATR): ν = 2922, 2871
˜
(aliph. C–H), 1622, 1590 (arom. C–C), 1513, 1455 (aliph. C–H), 1245,
1093 (C–O–C), 970, 826, 720 (arom. C–H) cm–1. MS (ESI, CHCl3/
MeOH): m/z = 741 [M + Na]+, 719 [M + H]+. MS (MALDI, Cl-CCA):
m/z = 719 [M + H]+. C48H50N2O4 (718.38): calcd. C 80.19, H 7.01, N
3.90; found C 80.27, H 7.26, N 3.73.
C
naphO(CH2)2CH2], 1.73 [mc, 4 H, CarO(CH2)2CH2], 1.54 (mc, 4 H,
CnaphOCH2CH2), 1.43 (mc, 4 H, CarOCH2CH2) ppm. * Assignment may
be reversed. 13C NMR (125 MHz, [D6]DMSO): δ = 157.1 (s, 2,6-Car),
156.9 (s, 7-Cnaph), 156.2 (s, 2-Cphen), 154.9 (s, 9-Cphen), 154.2 (2-Cnaph),
145.7 (s, 10b-Cphen), 145.5 (s, 10a-Cphen), 137.8 [d, CarO(CH2)3CH=, 2-
2,11,13,22-Tetraoxa-1(1,3,2)-benzena-12(2,7,1)-naphthalina-
23(2,9)-1,10-phenanthrolina-bicyclo[10.10.1]tricosaphane (rac-
19a): First nitrogen, then hydrogen were bubbled through a sus-
pension of palladium on charcoal (10 %, 29 mg, 27 μmol) in acid-
free dichloromethane/ethyl acetate (1:1, 15 mL) for 15 min each. A
solution of rac-18a (180 mg, 272 μmol) in acid-free dichloro-
methane/methanol (1:1, 10 mL) was added, and the mixture was
flushed with hydrogen for 1 h followed by stirring at room temp.
for 20 h under hydrogen. The suspension was filtered through basic
aluminium oxide (dichloromethane) and the solvent was evapo-
rated. The residue was filtered through a little magnesium sulfate
(dichloromethane) and the solvent was removed again to give rac-
19a (138 mg, 207 μmol, 76 %) as a yellow solid, m.p. 247–249 °C.
C
naphO(CH2)3CH=*1], 137.6 [d, 7-CnaphO(CH2)3CH=*1], 135.9 (d, 4-
Cphen), 135.2 (d, 7-Cphen), 134.2 (s, 8a-Cnaph), 129.7 (d, 4-Cnaph),
129.64 (d, 4-Car), 129.57 (d, 5-Cnaph), 127.05 (s, 6a-Cphen), 127.01 (s,
4a-Cphen), 126.4 (d, 6-Cphen), 126.1 (d, 5-Cphen), 125.9 (d, 3-Cphen),
125.6 (d, 8-Cphen), 124.2 (s, 4a-Cnaph), 123.7 (s, 1-Cnaph), 120.6 (s, 1-
Car), 115.7 (d, 6-Cnaph), 114.9 [t, 7-CnaphO(CH2)3CH=CH2], 114.8 [t, 2-
CnaphO(CH2)3CH=CH2], 114.6 [t, CarO(CH2)3CH=CH2], 112.7 (d, 3-
Cnaph), 105.8 (d, 3,5-Car), 104.5 (d, 8-Cnaph), 68.1 (t, 2-CnaphOCH2),
67.5 (t, CarOCH2), 66.4 (t, 7-CnaphOCH2), 29.39 [t, 7-CnaphO(CH2)2CH2],
29.36 [t, 2-CnaphO(CH2)2CH2], 29.27 [t, CarO(CH2)2CH2], 27.9 (t, 7-
C
naphOCH2CH2*2), 27.6 (t, CarOCH2CH2), 27.3 (t, 2-CnaphOCH2-
2
CH2*2) ppm. *1,
*
Assignments may be reversed, respectively. IR
(ATR): ν = 3073 (arom. C–H), 2939, 2873 (aliph. C–H), 1622, 1590
˜
1H NMR (600 MHz, CDCl3): δ = 8.33 (d, J = 8.1 Hz, 1 H, 4-CphenH),
3
(arom. C–C), 1510, 1455 (aliph. C–H), 1250, 1209, 1093, 1067 (C–O–
C), 991, 909, 855, 827 (arom. C–H) cm–1. MS (EI, 70 eV): m/z (%) =
718 (100) [M]+·, 677 (46) [M – C3H5]+, 663 (52) [M – C4H7]+, 649 (33)
[M – C5H9]+. MS (CI, isobutane): m/z (%) = 719 (17) [M + H]+. MS
(MALDI, Cl-CCA): m/z = 719 [M + H]+. C48H50N2O4 (718.38): calcd. C
80.19, H 7.01, N 3.90; found C 80.22, H 6.96, N 3.97.
3
8.25 (d, J = 8.2 Hz, 1 H, 7-CphenH), 7.89 (s, 2 H, 5,6-CphenH), 7.78 (d,
3J = 9.0 Hz, 1 H, 4-CnaphH), 7.69 (d, J = 8.1 Hz, 1 H, 3-CphenH), 7.67
3
(d, 3J = 9.0 Hz, 1 H, 5-CnaphH), 7.60 (d, J = 8.2 Hz, 1 H, 8-CphenH),
3
3
3
7.20 (t, J = 8.3 Hz, 1 H, 4-CarH), 7.15 (d, J = 9.0 Hz, 1 H, 3-CnaphH),
6.94 (dd, 3J = 9.0 Hz, 2J = 2.4 Hz, 1 H, 6-CnaphH), 6.67 (d, 2J = 2.4 Hz,
1 H, 8-CnaphH), 6.59 (d, 3J = 8.3 Hz, 1 H, 3-CarH*), 6.53 (d, 3J = 8.3 Hz,
2,11,13,22-Tetraoxa-1(1,3,2)-benzena-12(2,7,1)-naphthalina-
23(2,9)-1,10-phenanthrolinabicyclo[10.10.1]tricosaphane-6,17-
diene (rac-18a): Under nitrogen, 17 (260 mg, 362 μmol) and benz-
1 H, 5-CarH*), 4.15 (mc, 1 H, 2-CnaphOCHHa), 3.93–3.70 (m, 6 H, 2-Cnaph-
OCHHb, CarOCH2, 7-CnaphOCHHa), 3.62–3.57 (m, 1 H, 7-CnaphOCHHb),
1.70–0.51 (m, 24 H, CH2CH2CH2) ppm. * Assignment may be re-
ylidene-bis(tricyclohexylphosphine)dichlororuthenium (Grubbs versed. 13C NMR (151 MHz, CDCl3): δ = 158.4 (s, 2-Car*1), 157.8 (s, 7-
type I catalyst, 30 mg, 37 μmol) were dissolved in anhydrous di- Cnaph), 157.7 (s, 2-Cphen), 157.4 (s, 6-Car*1), 155.8 (s, 9-Cphen), 154.9
chloromethane (360 mL). The solution was stirred at room temp.
for 24 h, then the mixture was filtered through basic aluminium
oxide (dichloromethane/methanol, 98:2). Ethyl vinyl ether (15 mL)
was added, the mixture was stirred at room temp. for 10 min, and
(s, 2-Cnaph), 146.5 (s, 10b-Cphen), 146.2 (s, 10a-Cphen), 135.8 (d, 4-
Cphen), 135.2 (d, 7-Cphen), 134.9 (s, 8a-Cnaph), 129.8 (d, 4-Cnaph), 129.7
(d, 4-Car), 129.3 (d, 5-Cnaph), 127.5 (s, 4a-Cphen), 127.4 (s, 6a-Cphen),
126.7 (d, 6-Cphen*2), 126.6 (d, 3-Cphen*2), 126.3 (d, 8-Cphen*3), 126.1
the solvent was evaporated. The yellow-brown crude product was (d, 5-Cphen*3), 124.8 (s, 1-Cnaph), 124.7 (s, 4a-Cnaph), 120.9 (s, 1-Car),
purified by column chromatography (silica gel; dichloromethane/
116.5 (d, 6-Cnaph), 112.5 (d, 3-Cnaph), 106.1 (d, 5-Car*4), 105.6 (d, 3-
methanol, 98:2; Rf = 0.15–0.02) to give rac-18a (188 mg, 284 μmol, Car*4), 105.0 (d, 8-Cnaph), 69.7 (t, 2-CnaphOCH2), 69.3, 67.9 (2t, Car-
78 %) as a yellow solid, m.p. 148–152 °C. NMR spectra were meas-
ured (see the Supporting Information); however, due to signal over-
OCH2), 67.2 (t, 7-CnaphOCH2), 29.3, 28.8, 28.2, 27.8, 27.7, 27.4, 25.85,
2, 3,
4
25.80, 24.9, 24.8 (10t, CH2CH2CH2) ppm. *1,
* * * Assignments
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Full Paper
may be reversed, respectively. IR (ATR): ν = 2925, 2855 (aliph. C–H),
3J = 8.2 Hz, 1 H, 7-CphenH), 7.88 (s, 2 H, 5,6-CphenH), 7.77 (d, 3J =
˜
3
1623, 1589 (arom. C–C), 1510, 1456 (aliph. C–H), 1238, 1096 (C–O–
9.0 Hz, 1 H, 4-CnaphH), 7.68 (d, J = 8.9 Hz, 1 H, 5-CnaphH), 7.66 (d,
C), 854, 825, 719 (arom. C–H) cm–1. MS (ESI, CHCl3/MeOH): m/z =
3J = 8.2 Hz, 1 H, 3-CphenH), 7.60 (d, J = 8.2 Hz, 1 H, 8-CphenH), 7.19
3
689 [M + Na]+, 667 [M + H]+. MS (MALDI, Cl-CCA): m/z = 667 [M + (t, J = 8.3 Hz, 1 H, 4-CarH), 7.16 (d, J = 9.0 Hz, 1 H, 3-CnaphH), 6.96
3
3
H]+. C44H46N2O4 (666.35): calcd. C 79.25, H 6.95, N 4.20; found C
78.99, H 7.01, N 4.07.
(dd, J = 8.9 Hz, J = 2.4 Hz, 1 H, 6-CnaphH), 6.70 (d, J = 2.4 Hz, 1
3
2
2
3
3
H, 8-CnaphH), 6.57 (d, J = 8.3 Hz, 1 H, 3-CarH*), 6.56 (d, J = 8.3 Hz,
1 H, 5-CarH*), 4.04–3.94 (m, 2 H, 2-CnaphOCH2), 3.93–3.72 (m, 6 H,
CarOCH2, 7-CnaphOCH2), 1.68–1.31 (m, 8 H, OCH2CH2), 1.13–0.40 (m,
24 H, CH2CH2CH2) ppm. * Assignment may be reversed. 13C NMR
(125 MHz, CDCl3): δ = 158.2 (s, 2-Car*1), 158.0 (s, 6-Car*1), 157.8 (s,
7-Cnaph), 157.5 (s, 2-Cphen), 155.9 (s, 9-Cphen), 155.2 (s, 2-Cnaph), 146.8
(s, 10b-Cphen), 146.4 (s, 10a-Cphen), 135.9 (d, 4-Cphen), 135.1 (d, 7-
2,12,14,24-Tetraoxa-1(1,3,2)-benzena-13(2,7,1)-naphthalina-
25(2,9)-1,10-phenanthrolina-bicyclo[11.11.1]pentacosaphane
(rac-19b): Under nitrogen, cesium carbonate (707 mg, 2.17 mmol)
and anhydrous potassium carbonate (391 mg, 2.83 mmol) were sus-
pended in anhydrous N,N-dimethylformamide (86 mL). A solution
of 16 (250 mg, 560 μmol) and 1,9-dibromononane (228 μL, 320 mg,
1.12 mmol) in anhydrous N,N-dimethylformamide (40 mL) were
added dropwise by using a syringe driver at 65 °C over 15 h. The
suspension was then stirred at 65 °C for 1.5 h. After cooling to room
temp., the solid was filtered off and the solvent was evaporated.
The brown residue was dissolved in dichloromethane (40 mL) and
water (20 mL), the layers were separated and the aqueous layer was
extracted with dichloromethane (3 × 10 mL). The combined organic
layer was dried with magnesium sulfate and the solvent was evapo-
rated. The red-brown crude product was purified by column chro-
matography (silica gel; dichloromethane/ethyl acetate, 9:1; Rf =
0.29) to give rac-19b (121 mg, 174 μmol, 31 %) as a yellow solid,
m.p. 247–249 °C. 1H NMR (500 MHz, CDCl3): δ = 8.34 (d, 3J = 8.1 Hz,
Cphen), 135.0 (s, 8a-Cnaph), 129.7 (d, 4-Cnaph), 129.6 (d, 4-Car), 129.4
(d, 5-Cnaph), 127.65 (s, 6a-Cphen*2), 127.60 (s, 4a-Cphen*2), 126.6 (d, 6-
Cphen), 126.45 (d, 8-Cphen*3), 126.36 (d, 3-Cphen*3), 126.1 (d, 5-Cphen),
125.0 (s, 4a-Cnaph*4), 124.9 (s, 1-Cnaph*4), 121.3 (s, 1-Car), 115.9 (d, 6-
Cnaph), 113.0 (d, 3-Cnaph), 106.1 (d, 3-Car*5), 106.0 (d, 5-Car*5), 105.5
(d, 8-Cnaph), 70.0 (t, 2-CnaphOCH2), 69.4, 69.0, 67.8 (3t, OCH2), 29.0,
28.60, 28.56, 28.3, 27.6, 27.4, 27.33, 27.25, 27.24, 26.8, 26.6, 25.0,
2, 3,
24.8, 24.71, 24.69 (15t, CH2CH2CH2) ppm. *1,
* * *
4, *5 Assignments
may be reversed, respectively. IR (ATR): ν = 3061, 3037 (arom. C–H),
˜
2923, 2854 (aliph. C–H), 1622, 1588 (arom. C–C), 1455 (aliph. C–H),
1243, 1230, 1213 (C–O–C), 852, 823 (arom. C–H) cm–1. MS (ESI,
CHCl3/MeOH): m/z = 745 [M + Na]+, 723 [M + H]+. C48H54N2O4
(722.41): calcd. C 79.74, H 7.53, N 3.87; found: C 79.39, H 7.77, N
4.02.
3
1 H, 4-CphenH), 8.26 (d, J = 8.2 Hz, 1 H, 7-CphenH), 7.89 (s, 2 H, 5,6-
CphenH), 7.77 (d, 3J = 8.9 Hz, 1 H, 4-CnaphH), 7.69 (d, 3J = 8.1 Hz, 1
H, 3-CphenH), 7.68 (d, 3J = 9.0 Hz, 1 H, 5-CnaphH), 7.62 (d, 3J = 8.2 Hz,
2,7-Dimethoxynaphthalene (26):[30] In a flow of nitrogen, 2,7-di-
hydroxynaphthalene (25; 10.0 g, 62.5 mmol) was added to a 15 °C
solution of potassium hydroxide (8.72 g, 156 mmol) in water
(88 mL). Then dimethyl sulfate (12.5 mL, 132 mmol) was added to
the brown solution, while keeping the temperature under 20 °C.
The mixture was heated to 100 °C for 1 h. After cooling to room
3
3
1 H, 8-CphenH), 7.19 (t, J = 8.3 Hz, 1 H, 4-CarH), 7.17 (d, J = 8.9 Hz,
1 H, 3-CnaphH), 6.95 (dd, 3J = 9.0 Hz, 4J = 2.4 Hz, 1 H, 6-CnaphH), 6.58
(d, 4J = 2.4 Hz, 1 H, 8-CnaphH), 6.56 (d, 3J = 8.3 Hz, 2 H, 3,5-CarH),
4.17–3.67 (m, 8 H, OCH2), 1.70–0.50 (m, 28 H, CH2CH2CH2) ppm. 13
C
NMR (125 MHz, CDCl3): δ = 158.1 (s, 2-Car*1), 157.9 (s, 6-Car*1), 157.5
(s, 2-Cphen, 7-Cnaph), 155.9 (s, 9-Cphen), 154.9 (s, 2-Cnaph), 146.7 (10b- temp., the precipitate was washed with potassium hydroxide solu-
Cphen), 146.3 (10a-Cphen), 135.9 (d, 4-Cphen), 135.2 (d, 7-Cphen), 135.0 tion (2 , 30 mL) and water (30 mL). Then the solid was dissolved
M
(s, 8a-Cnaph), 129.7 (2d, 4-Car, 4-Cnaph), 129.4 (d, 5-Cnaph), 127.53 (s,
4a-Cphen), 127.49 (s, 6a-Cphen), 126.6 (d, 6-Cphen), 126.31 (d, 5-
C
in dichloromethane, washed with brine and dried with magnesium
sulfate. The solvent was evaporated and the crude product was
recrystallized from ethyl acetate to give 26 (6.17 g, 32.8 mmol, 53 %)
as a slightly brown solid, m.p. 138 °C. 1H NMR (500 MHz, CDCl3):
phen*2), 126.28 (d, 8-Cphen*2), 126.1 (d, 3-Cphen), 125.2 (s, 1-Cnaph),
124.9 (s, 4a-Cnaph), 121.0 (s, 1-Car), 116.5 (d, 6-Cnaph), 113.0 (d, 3-
Cnaph), 105.9 (d, 3-Car*3), 105.8 (d, 5-Car*3), 104.6 (d, 8-Cnaph), 69.12,
69.06, 68.4, 66.6 (4t, OCH2), 28.9, 28.82, 28.75, 28.6, 27.9, 27.3, 27.19,
3
4
δ = 7.65 (d, J = 9.0 Hz, 2 H, 4,6-CnaphH), 7.06 (d, J = 2.5 Hz, 2 H,
3
4
1,8-CnaphH), 6.99 (dd, J = 9.0 Hz, J = 2.5 Hz, 2 H, 3,5-CnaphH), 3.90
(s, 6 H, OCH3) ppm. 13C NMR (125 MHz, CDCl3): δ = 158.4 (s, 2,7-
Cnaph), 136.1 (s, 8a-Cnaph), 129.3 (d, 4,5-Cnaph), 124.4 (s, 4a-Cnaph),
2,
3
27.15, 26.8, 26.5, 25.3, 25.1, 24.4, 24.2 (14t, CH2CH2CH2) ppm. *1,
* *
Assignments may be reversed, respectively. IR (ATR): ν = 3957, 3028
˜
(arom. C–H), 2926, 2854 (aliph. C–H), 1622, 1587 (arom. C–C), 1511, 116.2 (d, 3,6-Cnaph), 105.4 (d, 1,8-Cnaph), 55.4 (q, OCH3) ppm. IR (ATR):
1456 (aliph. C–H), 1245, 1099 (C–O–C), 854, 824, 720 (arom. C–
ν = 3010 (arom. C–H), 2965, 2936 (aliph. C–H), 2836 (O–CH3), 1625,
1605, 1510 (arom. C–C), 1469, 1459, 1384 (aliph. C–H), 1230, 1211,
˜
H) cm–1. MS (MALDI, Cl-CCA): m/z = 695 [M + H]+. HRMS (FT-ICR):
calcd. for C46H51N2O4 [M + H]+: 695.384; found: 695.384 (Δ = 1025 (C–O–C), 863, 835, 777 (arom. C–H) cm–1. MS (EI, 70 eV): m/z
+
2 ppm).
(%) = 188 (100) [M]+·, 159 (4) [M – C2H6]+, 145 (46) [M – C2H6O]+,
130 (8) [M – C3H7]+·, 115 (8) [M – C3H6O2]+. MS (CI, isobutane): m/z
(%) = 189 (100) [M + H]+. C12H12O2 (188.08): calcd. C 76.57, H 6.43;
found: C 76.79, H 6.41.
2,13,15,26-Tetraoxa-1(1,3,2)-benzena-14(2,7,1)-naphthalina-
27(2,9)-1,10-phenanthrolina-bicyclo[12.12.1]heptacosaphane
(rac-19c): First nitrogen, then hydrogen were bubbled through a
suspension of palladium on charcoal (10 %, 35 mg, 33 μmol) in acid-
1-Bromo-2,7-dimethoxynaphthalene (27): The synthesis was car-
free dichloromethane/ethyl acetate (1:1, 15 mL) for 15 min each. A ried out in analogy to the procedure of Bagheri, Azizi and Saidi.[25]
solution of rac-18c (233 mg, 324 μmol) in acid-free dichloro-
methane/methanol (1:1, 20 mL) was added, and the mixture was
flushed with hydrogen for 1 h followed by stirring at room temp.
for 20 h under hydrogen. The suspension was filtered through basic
aluminium oxide (dichloromethane) and the solvent was evapo-
rated. The residue was filtered through a little magnesium sulfate
(dichloromethane) and the solvent was removed again. The crude
product was purified by column chromatography (silica gel; di-
chloromethane/ethyl acetate, 9:1; Rf = 0.39) to give rac-19c (188 mg,
Lithium perchlorate on silica gel (1:4, 4.26 g) and 2,7-dimethoxy-
naphthalene (26; 4.00 g, 21.3 mmol) were suspended in dichloro-
methane (250 mL). N-Bromosuccinimide (3.80 g, 21.4 mmol) was
added and the suspension was stirred at room temp. for 18 h. The
remaining solid was filtered off and washed with dichloromethane.
The solvent of the organic layer was then evaporated. The residue
was dissolved in acetonitrile and water was added. The yellow pre-
cipitate was filtered off and dissolved in dichloromethane. After sep-
aration from remaining water, the organic layer was dried with mag-
260 μmol, 80 %) as a white solid, m.p. 259–261 °C. 1H NMR nesium sulfate. The solvent was evaporated and the brown crude
(500 MHz, CDCl3): δ = 8.32 (d, 3J = 8.2 Hz, 1 H, 4-CphenH), 8.24 (d,
product was purified by column chromatography (silica gel; cyclo-
Eur. J. Org. Chem. 2016, 1119–1131
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hexane/ethyl acetate, 6:1; Rf = 0.36) and subsequent recrystalliza- (500 MHz, CDCl3): δ = 8.32 (d, 3J = 8.2 Hz, 1 H, 4-CphenH), 8.26 (d,
tion from methanol to give 27 (4.58 g, 17.2 mmol, 81 %) as colour-
3J = 8.1 Hz, 1 H, 7-CphenH), 7.86 (s, 2 H, 5,6-CphenH), 7.81 (d, 3J =
3
less needles, m.p. 80 °C. 1H NMR (500 MHz, CDCl3): δ = 7.72 (d, 3J =
8.9 Hz, 1 H, 4-CnaphH), 7.78 (d, J = 8.2 Hz, 1 H, 3-CphenH), 7.68 (d,
8.9 Hz, 1 H, 4-CnaphH), 7.67 (d, 3J = 8.9 Hz, 1 H, 5-CnaphH), 7.50 (d, 3J = 9.0 Hz, 1 H, 5-CnaphH), 7.63 (d, J = 8.1 Hz, 1 H, 8-CphenH), 7.26
3
4J = 2.4 Hz, 1 H, 8-CnaphH), 7.11 (d, 3J = 8.9 Hz, 1 H, 3-CnaphH), (t, J = 8.4 Hz, 1 H, 4-CarH), 7.19 (d, J = 8.9 Hz, 1 H, 3-CnaphH), 7.12
3
3
7.04 (dd, 3J = 8.9 Hz, 4J = 2.4 Hz, 1 H, 6-CnaphH), 4.02 (s, 3 H,
2-CnaphOCH3), 3.97 (s, 3 H, 7-CnaphOCH3) ppm. 13C NMR (125 MHz,
CDCl3): δ = 159.4 (s, 7-Cnaph), 154.4 (s, 2-Cnaph), 134.6 (s, 8a-Cnaph),
129.8 (d, 5-Cnaph), 128.6 (d, 4-Cnaph), 125.2 (s, 4a-Cnaph), 117.3 (d, 6-
(d, J = 2.4 Hz, 1 H, 8-CnaphH), 6.96 (dd, J = 9.0 Hz, J = 2.4 Hz, 1
4
3
4
H, 6-CnaphH), 6.61 (d, 3J = 8.4 Hz, 2 H, 3,5-CarH), 3.84 (s, 3 H, 2-
C
phenOCH3), 3.67 (s, 6 H, CarOCH3), 3.56 (s, 3 H, 7-CphenOCH3) ppm.
13C NMR (125 MHz, CDCl3): δ = 158.7 (s, 2,6-Car), 158.3 (s, 7-Cnaph),
Cnaph), 110.9 (d, 3-Cnaph), 107.6 (s, 1-Cnaph), 104.5 (d, 8-Cnaph), 57.0 156.8 (s, 2-Cphen), 155.8 (s, 2-Cnaph), 155.3 (s, 9-Cphen), 146.65 (s, 10a-
(q, 2-CnaphOCH3), 55.4 (q, 7-CnaphOCH3) ppm. IR (ATR): ν = 3003
C
phen*1), 146.61 (s, 10b-Cphen*1), 135.7 (d, 4-Cphen), 135.4 (d, 7-Cphen),
135.0 (s, 8a-Cnaph), 130.1 (d, 4-Cnaph), 129.8 (d, 4-Car), 129.4 (d, 5-
˜
(arom. C–H), 2965, 2935 (aliph. C–H), 2842 (O–CH3), 1621, 1598,
1508 (arom. C–C), 1459, 1447, 1381 (aliph. C–H), 1263, 1219 (C–O–
C), 1066 (C–Br), 1027 (C–O–C), 830, 772 (arom. C–H) cm–1. MS (EI,
70 eV): m/z (%) = 268, 266 (97, 100) [M]+·, 225, 223 (45, 46) [M –
C
naph), 127.7 (s, 4a-Cphen*2), 127.5 (s, 6a-Cphen*2), 126.71, 126.66 (2d,
3-Cphen, 6-Cphen*3), 126.26, 126.25 (2d, 5-Cphen*3, 8-Cphen), 125.1 (s,
4a-Cnaph), 124.4 (s, 1-Cnaph), 120.9 (s, 1-Car), 116.3 (d, 6-Cnaph), 111.7
CH3O]+, 172 (12) [M – CH3Br]+·, 157 (13) [M – C2H5Br]+. MS (CI, iso- (d, 3-Cnaph), 105.2 (d, 3,5-Car), 104.2 (d, 8-Cnaph), 57.2 (q, 2-
butane): m/z (%) = 269, 267 (100, 97) [M + H]+. C12H11BrO2 (265.99):
CnaphOCH3), 56.5 (q, CarOCH3), 55.2 (q, 7-CnaphOCH3) ppm. *1,*,2*3
calcd. C 53.96, H 4.15; found C 54.31, H 4.08.
Assignments may be reversed, respectively. IR (ATR): ν = 3051 (arom.
˜
C–H),2953(aliph.C–H),2833(O–CH3),1622,1587,1496(arom.C–C),1470
(aliph. C–H), 1249, 1225, 1214, 1106, 1070, 1028 (C–O–C), 854, 825,
779 (arom. C–H) cm–1. MS (EI, 70 eV): m/z (%) = 502 (100) [M]+·, 487
(50) [M – CH3]+. MS (CI, isobutane): m/z (%) = 503 (100) [M + H]+.
C32H26N2O4 (502.57): calcd. C 76.48, H 5.21, N 5.57; found C 76.59,
H 5.25, N 5.62.
Pinacol 2,7-Dimethoxynaphthylboronate (28): Under nitrogen, 1-
bromo-2,7-dimethoxynaphthalene (27; 1.0 g, 3.7 mmol) was dis-
solved in anhydrous tetrahydrofuran (25 mL) and cooled to –78 °C.
n-Butyllithium (2.5
M in hexanes, 1.65 mL, 4.12 mmol) was added
and the mixture was stirred at –78 °C for 1 h. Isopropoxyboronic
acid pinacol ester (1.53 mL, 1.40 g, 7.52 mmol) was then added and
the mixture was stirred for 15 h while warming slowly to room
temp. Water was added, the layers were separated, and the aqueous
layer was extracted with diethyl ether (4 × 15 mL). The combined
organic layer was washed with brine and dried with magnesium
sulfate. The solvent was evaporated and the slightly orange residue
was purified by column chromatography (silica gel; cyclohexane/
ethyl acetate, 6:1; Rf = 0.29) to give 28 (871 mg, 2.77 mmol, 74 %)
as a white solid, m.p. 131 °C. 1H NMR (500 MHz, CDCl3): δ = 7.75 (d,
Calculations: All calculations were performed using the program
TURBOMOLE.[31] The geometry of (M)-19a was fully optimized in
the gas phase using the DFT potential B3LYP-D3,[18] which includes
an additional dispersion correction.[19] As basis set, 6-31G*[20] was
employed. For all calculations, the default thresholds implemented
in TURBOMOLE were used. The obtained geometry of (M)-19a was
characterized as minimum by a subsequent frequency calculation
using B3LYP-D3/6-31G*. The CD spectrum of (M)-19a was simulated
with the time-dependent density functional theory (TD-DFT), using
the B3LYP functional and the 6-31G* basis set. The TD-DFT calcula-
tion was performed at the optimized ground-state geometry of (M)-
19a, and the energy, oscillator strength, and rotatory strength were
calculated for each of the 100 lowest singlet excitations. The CD
spectrum was simulated by overlapping Gaussian functions for each
transition, for which the width of the Gaussian function was fixed
at 10 nm. The intensity of the simulated CD spectrum was scaled
to the experimental values.
3
3J = 9.0 Hz, 1 H, 4-CnaphH), 7.63 (d, J = 9.0 Hz, 1 H, 5-CnaphH), 7.31
(d, 4J = 2.5 Hz, 1 H, 8-CnaphH), 7.04 (d, 3J = 9.0 Hz, 1 H, 3-CnaphH),
6.96 (dd, 3J = 9.0 Hz, 4J = 2.5 Hz, 1 H, 6-CnaphH), 3.90 (s, 3 H, 2-Cnaph
-
OCH3), 3.88 (s, 3 H, 7-CnaphOCH3), 1.47 (s, 12 H, CCH3) ppm. 13C NMR
(125 MHz, CDCl3): δ = 162.5 (s, 2-Cnaph), 158.3 (s, 7-Cnaph), 138.8 (s,
8a-Cnaph), 131.6 (d, 4-Cnaph), 129.7 (d, 5-Cnaph), 124.6 (s, 4a-Cnaph),
116.3 (d, 6-Cnaph), 110.5 (d, 3-Cnaph), 105.4 (d, 8-Cnaph), 83.9 (s, CCH3),
56.7 (q, 2-CnaphOCH3), 55.1 (q, 7-CnaphOCH3), 25.1 (q, CCH3) ppm. IR
(ATR): ν = 2976, 2836 (aliph. C–H), 1629, 1581 (arom. C–C), 1505,
˜
1460, 1430, 1335, 1314 (aliph. C–H), 1243, 1221, 1140, 1127, 1072
(C–O–C), 845, 830, 775 (arom. C–H) cm–1. MS (ESI, CHCl3/MeOH):
m/z = 337 [M + Na]+, 314 [M]+·, 300 [M – CH2]+·. C18H23BO4 (314.17):
calcd. C 68.81, H 7.38; found C 68.89, H 7.37.
General Procedure for Cyclopropanation: Under nitrogen, cop-
per(I) triflate benzene complex [ca. 0.2 to 0.8 mg ( 0.01 mg)] was
placed in a vial. One of the ligands 19a–c or 30 [2.1 equiv.; based
on copper(I)] and indene (21, 350 equiv.) dissolved in degassed,
anhydrous 1,2-dichloroethane (0.8 mL) were then added. After addi-
tion of ethyl diazoacetate (20, 50 equiv.), the mixture was stirred at
room temp. for 20 h. The mixture was then filtered through silica
gel with dichloromethane as eluent. Most of the solvent was evapo-
rated in vacuo until ca. 1.5 mL remained. After addition of n-hexa-
decane [ca. 1 to 1.5 mg/mL ( 0.01 mg)] as GC standard, the pro-
ducts were analyzed by GC.
2-(2,7-Dimethoxynaphthyl)-9-(2,6-dimethoxyphenyl)1,10-phen-
anthroline (30): Under nitrogen, 2-chloro-9-(dimethoxyphenyl)-
1,10-phenanthroline (29; 351 mg, 1.00 mmol), 2,7-dimethoxy-
naphthylboronic acid pinacol ester (28; 471 mg, 1.50 mmol), [1,1′-
bis(diphenylphosphanyl)ferrocene]dichloropalladium(II) (122 mg,
150 μmol) and barium hydroxide octahydrate (877 mg, 2.78 mmol)
were dissolved in 1,2-dimethoxyethane (60 mL) and water (15 mL).
The suspension was heated to 70 °C for 21 h. After cooling to room
temp., dichloromethane and water (50 mL each) were added and
the layers were separated. The aqueous layer was extracted with
dichloromethane (5 × 50 mL) and the combined organic layer was
washed with half conc. aqueous sodium chloride solution, dried
with magnesium sulfate and the solvent was evaporated. The dark-
brown residue was filtered through basic aluminium oxide with di-
chloromethane. After evaporation of the solvent, the yellow crude
product was purified by column chromatography (silica gel; di-
chloromethane/methanol, 98:2; Rf = 0.07) to give 30 (211 mg,
429 μmol, 42 %) as a yellow-brown solid, m.p. 259 °C. 1H NMR
Keywords: Macrocycles · Chiral resolution · Circular
dichroism · Stereoselectivity · Cyclopropanation
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Full Paper
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Received: October 6, 2015
Published Online: January 22, 2016
Eur. J. Org. Chem. 2016, 1119–1131
www.eurjoc.org
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© 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim