Synthesis of Triphenylene-Based Triptycenes via Suzuki-Miyaura Cross-Coupling and Subsequent Scholl Reaction

Article abstract of DOI:10.1021/acs.joc.5b01520

A two-step method (Suzuki-Miyaura cross-coupling, followed by Scholl oxidation) to triphenylene-based triptycenes is described, rendering a variety of -extended triptycenes accessible in high yields and without the necessity of column chromatography purif

Full text of DOI:10.1021/acs.joc.5b01520

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Note
Synthesis of Triphenylene based Triptycenes via Suzuki-
Miyaura Cross-Coupling and Subsequent Scholl Reaction
Dennis Reinhard, Frank Rominger, and Michael Mastalerz
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.5b01520 • Publication Date (Web): 20 Aug 2015
Downloaded from http://pubs.acs.org on August 24, 2015
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Synthesis of Triphenylene based Triptycenes via Suzukiꢀ
Miyaura CrossꢀCoupling and Subsequent Scholl Reaction
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Dennis Reinhard, Frank Rominger and Michael Mastalerz*
OrganischꢀChemisches Institut, RuprechtꢀKarlsꢀUniversität Heidelberg, Im Neuenheimer Feld 273, 69120
Heidelberg, Germany, eꢀmail: michael.mastalerz@oci.uniꢀheidelberg.de
Abstract:
A twoꢀstep method (SuzukiꢀMiyaura cross coupling followed by second Scholl oxidation) to
triphenylene based triptycenes is described, rendering a variety of πꢀextended triptycenes
accessible in high yields and without the necessity of column chromatography purification.
The versatility of this reaction has been demonstrated in the synthesis of a supertriptycene in
only four steps and high yields.
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Triptycenes with extended conjugated πꢀplanes have gained interest due to their high
intramolecular free volume (IMFV)1 as precursors for 1D and 2D porous polymers,2,3
supramolecular porous materials4 such as organic molecules with intrinsic microporosities
(OMIMs), fluorescent markers for in vivo studies,5 and for organic electronics.6 The most
frequently used reactions to construct such πꢀextended triptycenes are condensation reactions,
e.g. of diketones with diamine moieties.7 Examples of πꢀextended triptycenes with exclusively
aromatic hydrocarbon scaffolds are much rarer.1,8 In 2009 King and coworkers have reported
for the first time triphenylene based triptycenes (TBTs), which have been synthesized by the
reaction of hexabromotriptycene 1 with biphenylene zirconium reagents to give the
corresponding TBTs in 9% yield.9 Later, the yield could be improved to 28% by using bisꢀ
(tertꢀbutyl)ꢀbiphenylene stannane instead of the corresponding zirconium reagent in a
palladiumꢀcatalyzed reaction.10 However, the scope of these reactions is limited to three
compounds and the yields are not satisfying. Furthermore one has to take into account that the
required organometallic species first have to be synthesized in a multiple step sequence and
that the zirconium reagents are chemically labile.11
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It is well known that substituted triphenylenes can be synthesized from the corresponding oꢀ
terphenyls either by photoꢀirradiation in the presence of an oxidant such as I2,12 or by using
organic or metal based oxidative reagents, such as DDQ or FeCl3,13,14 often referred to as the
Scholl oxidation.15 In general, triphenylenes can be synthesized in high yields by the Scholl
oxidati on, if some guidelines concerning substitution effects are taken into account.16
Since oꢀterphenyls are easily accessible by twofold SuzukiꢀMiyaura crossꢀcoupling of 1,2ꢀ
dibromoarenes with arylboronic esters or acids,17 we developed a twoꢀstep method from
hexabromotriptycene 1 to synthesize TBTs, generally in higher yields than by previously
described methods. In addition, in most cases no column chromatographic workup procedures
were necessary.
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The first step of the reaction sequence was the sixfold palladium catalyzed transformation of
hexabromotriptycene 13 to the corresponding tris(terphenyls) 3aꢀ3g (Scheme 1). All
compounds could be isolated in yields of 61ꢀ95%. With the exception for
dodecamethoxyterphenyl 3f, no column chromatographic purification was necessary: after
dispersing the crude products in methanol and sonicating the suspension, the white solids
were collected by filtration, washed with methanol and nꢀpentane, and precipitated from
CHCl3 and MeOH to give compounds 3aꢀ3g in pure form. This was prooved by NMR
spectroscopy and elemental analyses (see Experimental Section and Supporting Information).
Compounds 3a and 3b have been additionally characterized by single crystal Xꢀray analysis
(see Supporting Information). To directly compare this method with the methods by Benjamin
King and coworkers,9,10 we first investigated compound 4a in the Scholl reaction. The
oxidation reaction was performed in an analogous manner to a protocol of Rathore et al.,13
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o
where methanesulfonic acid was added dropwise to a cooled solution (0 C) of 3a in dry
DCM, followed by the addition of 4.5 to 5 equiv. DDQ in one portion. After 10ꢀ15 min the
reaction was quenched and the crude product washed with methanol, nꢀhexane and nꢀpentane
to give after drying 62% of 3a as an offꢀwhite solid. The combined yield of 43% is
significantly higher than by the ‘zirconium or stannylene routes’ published before.9,10
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Scheme 1. Twoꢀstep synthesis of triphenylene triptycenes. For detailed reaction
conditions, see Experimental Section.
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a 4g was the observed main product but could not be isolated by common methods.
It has previously been shown that the position of the tertꢀbutyl group has only a minor effect
on the performance of the Scholl reaction and also inhibits vicinal reactions and
polymerization processes.16 Therefore we tested 3b under the same cyclization conditions as
3a and obtained the corresponding triphenylene compound 4b in an even higher yield of 71%.
Substrates bearing methoxy groups in paraꢀ or orthoꢀposition to the formed CꢀC bonds can
usually be converted in very high, sometimes quantitative yields in the oxidative CꢀC
coupling.13 Indeed, the hexamethoxy compound 3c and the veratrole derivative 3e were
converted to the corresponding triphenylenes 4c and 4e in 51% and 48% yield, respectively.
For 4e single crystals of sufficient quality for analysis by Xꢀray diffraction have been grown
from chloroform (see Figure 1, for crystallographic data see Supporting Information).
Through πꢀπꢀstacking (the closest distance of two atoms of adjacent πꢀplanes is d = 3.55 Å) 4e
is packed in a manner that large threeꢀdimensional voids (blue surface in Figure 1) are formed,
making the compound interesting as a precursor for porous supramolecular solids, which will
be studied and reported in due course.
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Figure 1. Xꢀray structure analysis of triphenylene triptycene 4e. a) and b) packing of two
adjacent molecules by πꢀπ stacking; c) voids (blue) of the crystal for a 3 x3 x 3 unit cell
described by the Connolly surface area for a probe with radius 1.2 Å. Enclathrated
chloroform molecules have been omitted for clarity.
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Rathore et al. have also reported that terphenyls with methoxy groups meta to the formed CꢀC
bond can be converted under typical Scholl conditions in 60% yield.13 However, when we
tried to apply these conditions for 3d, the starting material was fully consumed, but no
threefold oxidized product 4d was detected at all. Neither changing the acid from MeSO3H to
BF3·Et2O in the DDQ oxidation reaction, nor using anhydrous FeCl3 in nitromethane as
oxidative reagent led to isolable amounts of 4d. These observations are in accordance to the
guidelines provided before for Scholl oxidation.16 A similar result has been found when
applying the DDQ methods for compound 3f, where each crossꢀcoupled aromatic ring bears
methoxy groups in the 3ꢀ and 5ꢀposition. No formation of 4f was detected following the above
described procedure. While with MeSO3H the reaction gave an unidentifiable product mixture,
with BF3·Et2O only starting material was isolated. The conversion of nonꢀsubstituted
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terphenyl 3g to 4g is hampered, probably because of a low solubility of intermediates and the
product. Although by 1H NMR spectroscopy of the crude product the formation of 4g as main
product has been observed (Supporting Information), the compound could not be purified by
common methods. This once more confirms the results for unsubstituted terphenyls in Scholl
oxidation reactions made before by King et al. It should also be mentioned that for 4g, the
zirconium method of King is the method of choice because no intermolecular oxidative
coupling can occur.9
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To demonstrate the applicability of the new route, we envisioned to use it for the synthesis of
supertriptycene congener 8 in only four steps (Scheme 2).8 Triptycenyl pinacolboronate 6 was
accessible in 70% yield from 2ꢀbromotriptycene 5, which was synthesized according to an
early described procedure of Friedman and Logullo, in 16% yield by a DielsꢀAlder reaction of
anthracene and 5ꢀbromo anthranilic acid.18 SuzukiꢀMiyaura crossꢀcoupling of 6 with
hexabromide 1 gave hexatriptycenyl triptycene 7 in 84% yield. The subsequent oxidative
cyclodehydrogenation of 7 gave 8 in 74% yield. As described above, no column
chromatography was necessary for the purification of both compounds. It is worth mentioning,
that no formation of other regioisomers of 8 has been observed, which most probably can be
explained by the fusedꢀorthoꢀeffect,19 which suppresses the oxidative bond formation ortho to
the bridgeheads.
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Scheme 2. Synthesis of supertriptycene 8
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Conclusions
To conclude, we have presented a twoꢀstep method, which allows access to triphenylene
triptycenes in high yields. In almost all cases even without applying column chromatographic
purifications. In accordance to observations made before for the Scholl reaction, only
terphenyls with a certain substitution pattern of electronꢀdonating groups allow a good
conversion to the final products. Larger structures, such as supertriptycene 8 can be
synthesized by this method in high yields.
Experimental Section
General remarks: All reagents including the arylboronic acids 2aꢀg and solvents were
commercially available and used without further purification. Hexabromotriptycene 1 was
synthesized analog to the literature known procedure from King et al.3 For thin layer
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chromatography Silica gel 60 F254 plates were used and examined under UVꢀlight irradiation
(254 nm and 365 nm). Flash column chromatography was performed on flash silica gel
(particle size: 0.04ꢀ0.063 mm) using light petroleum ether, toluene, ethyl acetate and DCM.
Melting points are not corrected. NMR spectra were recorded on 600 MHzꢀ (1H NMR:
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600 MHz; C NMR: 151 MHz), 500 MHzꢀ (1H NMR: 500 MHz; C NMR: 126 MHz), 400
MHzꢀ (1H NMR: 400 MHz; 13C NMR: 101 MHz), and 300 MHzꢀspectrometers (1H NMR:
300 MHz, 13C NMR: 75 MHz) at 298 K, unless otherwise mentioned. Chemical shifts (δ) are
reported in parts per million (ppm) relative to traces of CHCl3 (δH = 7.26 ppm, δC = 77.16 ppm)
or C2D2Cl4 (δH = 5.963 ppm, δC = 73.78 ppm) in the corresponding deuterated solvent. IRꢀ
spectra were recorded on a Fourier Transform spectrophotometer equipped with a Ge ATR
crystal. UVꢀvis spectra were recorded on doubleꢀbeam UVꢀvis spectrophotometers utilizing
either double or single monochromators and photomultiplier tube detectors. MS and HRMS
(MALDI and DART) experiments were carried out in positive mode on a Fourier Transform
Ion Cyclotron Resonance (FTꢀICR) mass spectrometer equipped with a 9.4 T superconducting
magnet and interfaced to a dual ESI/MALDI source. Crystal structure analysis was
13
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accomplished on a diffractometer with a molybdenum source (λ(MoKα) = 0.71073 Å). Data
processing and absorption correction (SADABS)20 were accomplished by standard methods.
The structures were solved by direct methods and refined by full matrix least squares using
SHELXL software.21 All nonꢀhydrogen atoms were refined using anisotropic thermal
parameters, hydrogen atoms were treated using appropriate riding models. All
crystallographic information files (CCDC 1409998 (3a), CCDC 1409999 (3b) and CCDC
1410000 (4e)) have been deposited in the Cambridge Crystallographic Data Centre and can be
downloaded free of charge via www.ccdc.camac.uk/data_request/cif.
2ꢀbromotriptycene 5:18 To a refluxing solution of anthracene (4.13 g, 23.1 mmol, 1.00 eq.) in
MeCN (90 mL), solutions of isoamylnitrite (3.43 mL, 25.5 mmol, 1.10 eq.) in MeCN (1.5 mL)
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and 5ꢀbromoanthranilic acid (5.50 g, 25.5 mmol, 1.10 eq.) in 120 mL of 5:1 (v/v)
MeCN/diglyme were added concurrently over a period of 2 hours. The mixture was then
refluxed another 2 hours until MeCN was distilled off. After cooling to r.t. 50 mL of 4:1 (v/v)
MeOH/H2O were added. Crystallized anthracene was then removed by filtration. The mother
liquor was left over night and the precipitate filtered off. The offꢀwhite crude product was
further purified by column chromatography (SiO2; light petroleum ether/DCM 20:1) to give 5
as a white powder (1.22 g, 3.65 mmol, 16%): m.p. 159ꢀ160 °C; 1H NMR (300 MHz, CDCl3) δ
7.52 (d, J = 1.8, 1H), 7.38 (dd, J = 5.3, 3.2, 4H), 7.24 (d, J = 7.9, 1H), 7.11 (dd, J = 7.8, 1.9,
1H), 7.01 (dd, J = 5.3, 3.2, 4H), 5.39 (s, 1H), 5.37 (s, 1H) ppm; 13C NMR (75 MHz, CDCl3) δ
147.8, 144.9, 144.7, 144.6, 128.1, 127.0, 125.6, 125.5, 125.2, 123.9, 123.8, 118.7, 53.9, 53.7
ppm; HRMS (DART) m/z: [M]+ Calcd for C20H13Br 332.01951; Found 332.01915. The
analytical data are in accordance to those published before.18,22
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2ꢀtriptycenylboronic acid pinacol ester 6: In an ovenꢀdried and argonꢀpurged Schlenk flask,
2ꢀbromotriptycene 5 (1.00 g, 3.00 mmol, 1.00 eq.) was dissolved in dry THF (10 mL) and nꢀ
BuLi (1.6M in hexanes, 2.06 mL, 1.10 eq.) was added dropwise at ꢀ78 °C. After stirring for 2
hours at the same temperature, isopropoxyboronic acid pinacol ester (0.80 mL, 3.90 mmol,
1.3 eq.) was added and the mixture was warmed to r.t. over night. The reaction was quenched
by addition of sat. aq. NH4Cl solution (15 mL). After phase separation and extraction with
DCM (3 x 15 mL), the organic layer was washed twice with H2O and brine, dried over
MgSO4 and removed from the solvent in vacuum to give the crude product as a colorless
residue. Purification via flash column chromatography on silica gel (light petroleum
ether/ethyl acetate 40:1) yielded 6 as a white powder (799 mg, 2.10 mmol, 70%): m.p. 266ꢀ
1
268 °C; H NMR (400 MHz, CDCl3) δ 7.83 (s, 1H, Hꢀ1), 7.48 (dd, J = 7.3, 1.0, 1H, Hꢀ3),
7.40 (d, J = 7.3, 1H, Hꢀ4), 7.38 – 7.32 (m, 4H, Hꢀ5,8,11,14), 6.97 (m, 4H, Hꢀ6,7,12,13), 5.43
(s, 1H, Hꢀ10), 5.42 (s, 1H, Hꢀ9) ppm; 13C NMR (101 MHz, CDCl3) δ 148.7 (Cꢀ4a), 145.3 (Cꢀ
8a,10a,10b,14a), 145.0, 144.8 (Cꢀ9a), 132.5 (Cꢀ3), 129.6 (Cꢀ1), 125.4 (Cꢀ6,7,12,13), 125.3
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(Cꢀ6,7,12,13), 123.8 (Cꢀ5,8,11,14), 123.8 (Cꢀ5,8,11,14), 123.3 (Cꢀ4), 83.8 (OC(CH3)2), 54.5
(Cꢀ10), 54.2 (Cꢀ10), 25.0 (ꢀCH3) ppm; FT IR (ATR): ꢀȬ 3073 (w), 2991 (w), 2981 (w), 2953
(w), 1615 (w), 1603 (w), 1572 (w), 1493 (w), 1458 (m), 1417 (m), 1385 (m), 1372 (m), 1352
(s), 1327 (m), 1311 (m), 1291 (m), 1270 (m), 1215 (w), 1195 (w), 1166 (m), 1146 (s), 1121
(m), 1109 (w), 1097 (w), 1070 (m), 1022 (w), 1005 (w), 983 (w), 962 (w), 944 (w), 926 (w),
913 (w), 889 (w), 877 (w), 858 (m), 830 (w), 797 (w), 771(w), 750 (s), 738 (s), 701 (w), 683
(m), 650 (m), 634 (m), 624 (m), 612 (w) cmꢀ1; HRMS (DART) m/z: [M+NH4]+ Calcd for
C26H29BNO2 398.22904; Found 398.22794. Anal. calcd for C26H25BO2·H2O: C, 78.40, H,
6.83. Found: C, 78.76, H, 6.57.
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General procedure for SuzukiꢀMiyaura type cross coupling reactions (GP1):
In a screw capped vessel hexabromotriptycene 1 (250 mg, 344 µmol, 1.00 equiv.) and
arylboronic acid 2aꢀg (6.60ꢀ9.00 equiv.) were given to 10 mL of a degased 1:1ꢀmixture (v/v)
of THF and 1
M aq. K2CO3ꢀsolution. After addition of Pd2dba3 (37.8 mg, 41 µmol, 12 mol%)
and HP(tBu)3BF4 (29.9 mg, 103 µmol, 30 mol%), the vessel was purged with Argon and the
mixture stirred for 16 h at 80 °C. After cooling to r.t. EtOAc (10 mL) was added and the
phases were separated. The organic layer was washed with saturated aqueous NH4Clꢀsolution,
H2O and brine, dried over MgSO4 and solvents were evaporated in vacuum to give the crude
product as a yellow residue. After dispersing in methanol, sonication and filtration, the
product was washed with MeOH (3 x 10 mL) and pentane (3 x 20 mL) to give 3aꢀg as a white
powder.
2,3,6,7,12,13ꢀHexaꢀ((3’ꢀtertꢀbutyl)phenyl)triptycene
3a:
According
to
GP1
hexabromotriptycene 1 and 3ꢀ(tertꢀbutyl)phenylboronic acid 2a (500 mg, 2.84 mmol, 7.8 eq.)
gave after workup 3a as a colorless solid (266 mg, 0.25 mmol, 70%): m.p. 351 °C (under
1
dec.); H NMR (600 MHz, CDCl3): δ 7.59 (s, 6H, triptꢀH), 7.19ꢀ7.14 (m, 12H, ArꢀHꢀ4’,5’),
7.04 (m, 6H, ArꢀHꢀ6’), 6.95 (m, 6H, ArꢀHꢀ2’), 5.69 (s, 2H, bridgeheadꢀH), 1.06 (s,
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54H, ꢀC(CH3)3) ppm; C NMR (151 MHz, CDCl3): δ 150.4 (ArCꢀC(CH3)), 144.3 (triptC),
141.3 (triptCꢀAr), 138.6 (ArCꢀ1’), 128.3 (ArCꢀ2’), 127.8 (ArCꢀ5’), 126.7 (ArCꢀ6’), 125.9
(triptCꢀH), 123.1 (ArCꢀ4’), 53.4 (bridgeheadꢀC), 34.5 (ArꢀC(CH3)3), 31.3 (ArꢀC(CH3)3) ppm;
FT IR (ATR): ꢀȬ 2961 (m), 2904 (w), 2867 (w), 1737 (w), 1603 (w), 1580 (w), 1460 (m), 1415
(w), 1362 (m), 1268 (w), 1217 (w), 1203 (w), 1093 (w), 893 (w), 865 (w), 795 (s), 708 (s)
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cmꢀ1; UVꢀvis max/nm 251 (5.18) sh 292 (4.59); HRMS (MALDI) m/z: [M]+ Calcd for C80H86
λ
1046.67240; Found 1046.67117. Anal. calcd for C80H86·1/3H2O: C, 91.21, H, 8.29. Found: C,
91.22, H, 8.14.
2,3,6,7,12,13ꢀHexaꢀ((4’ꢀtertꢀbutyl)phenyl)triptycene
3b:
According
to
GP1
hexabromotriptycene 1 and 4ꢀ(tertꢀbutyl)phenylboronic acid 2b (544 mg, 2.84 mmol, 9.0 eq.)
gave after workup 3b as a colorless solid (302 mg, 0.29 mmol, 84%): m.p. 297 °C (under
dec.); 1H NMR (600 MHz, CDCl3) δ 7.51 (s, 6H, triptꢀH), 7.17 (d, J = 8.4 Hz, 12H, ArꢀHꢀ3’),
7.00 (d, J = 8.4 Hz, 12H, ArꢀHꢀ2’), 5.57 (s, 2H, bridgeheadꢀH), 1.27 (s, 54H, ꢀC(CH3)3) ppm;
13C NMR (151 MHz, CDCl3) δ 149.1 (ArCꢀC(CH3)), 144.1 (triptC), 138.7 (ArCꢀ1’), 137.7
(triptCꢀAr), 129.7 (ArCꢀ2’), 126.1 (triptCꢀH), 124.7 (ArCꢀ3’), 53.4 (bridgeheadꢀC), 34.5
(ArꢀC(CH3)3), 31.5 ppm (ArꢀC(CH3)3); FT IR (ATR) ͪȬ 3028 (w), 2961 (m), 2904 (w), 2867
(w), 1515 (w), 1462 (s), 1417 (w), 1393 (w), 1362 (m), 1268 (m), 1201 (w), 1113 (m), 1013
(w), 944 (w), 901 (w), 854 (w), 834 (s), 826 (s), 801 (w), 759 (w), 750 (w), 712 (w), 667 (w)
cmꢀ1; UVꢀvis max/nm 254 (5.15) sh 292 (4.47); HRMS (MALDI) m/z: [M]+ Calcd for C80H86
λ
1046.67240; Found 1046.67203. Anal. calcd for C80H86·1/3H2O: C, 91.21, H, 8.29. Found: C,
91.27, H, 8.28.
2,3,6,7,12,13ꢀHexaꢀ(3’ꢀmethoxyphenyl)triptycene
3c:
According
to
GP1
hexabromotriptycene 1 and 3ꢀmethoxyphenylboronic acid 2c (340 mg, 2.27 mmol, 6.6 eq.)
gave after workup 3c as an offꢀwhite solid (193 mg, 0.22 mmol, 63%): m.p. 248 °C; 1H NMR
(600 MHz, CDCl3): δ 7.56 (s, 6H, triptꢀH), 7.11 (t, J = 7.9 Hz, 6H, ArꢀHꢀ5’), 6.72 (m, 12H,
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ArꢀHꢀ4’,6’), 6.62 (m, 6H, ArꢀHꢀ2’) 5.65 (s, 2H, bridgeheadꢀH), 3.59 (s, 18H, OCH3) ppm;
13C NMR (151 MHz, CDCl3): δ 159.2 (ArCꢀOMe), 144.3 (triptꢀC), 142.9 (ArꢀCꢀ1’), 137.8
(triptCꢀAr), 129.0 (ArCꢀ5), 125.1 (triptCꢀH), 122.5 (ArCꢀ4’/6’), 115.1 (ArCꢀ2’), 112.9 (ArCꢀ
4’/6’), 55.2 (OCH3), 53.3 (bridgeheadꢀC) ppm; FT IR (ATR): ꢀȬ 2955 (w), 2936 (w), 2832 (w),
1601 (s), 1578 (s), 1488 (w), 1466 (s), 1429 (m), 1389 (w), 1319 (w), 1287 (s), 1262 (m),
1242 (m), 1209 (s), 1177 (m), 1034 (s), 995 (w), 860 (m), 785 (s), 703 (s), 634 (w) cmꢀ1; UVꢀ
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60
vis
λ
max/nm 248 (5.04), 283 (4.55); HRMS (MALDI) m/z: [M]+ Calcd for C62H50O6
890.36019; Found 890.35953. Anal. calcd for C62H50O6: C, 83.57, H, 5.66. Found: C, 83.34,
H, 5.65.
2,3,6,7,12,13ꢀHexaꢀ(4’ꢀmethoxyphenyl)triptycene
3d:
According
to
GP1
hexabromotriptycene 1 and 4ꢀmethoxyphenylboronic acid 2d (361 mg, 2.40 mmol, 7.0 eq.)
gave after workup and precipitation from CHCl3 with MeOH 3d as an offꢀwhite solid (270 mg,
1
0.30 mmol, 88%): m.p. 241 °C; H NMR (600 MHz, CDCl3): δ 7.48 (s, 6H, triptꢀH), 7.01 (d,
J = 8.7 Hz, 12H, ArꢀHꢀ3’), 6.74 (d, J = 8.8 Hz, 12H, ArꢀHꢀ2’), 5.59 (s, 2H, bridgeheadꢀH),
3.77 (s, 18H, OCH3) ppm; 13C NMR (151 MHz, CDCl3): δ 158.3 ppm (ArCꢀOMe), 144.1
(triptꢀC), 137.3 (triptCꢀAr), 134.3 (ArCꢀ1’), 131.1 (ArCꢀ3’), 126.1 (triptCꢀH), 113.5 (ArCꢀ2’),
55.3 (OꢀCH3), 53.3 (bridgeheadꢀC) ppm; FT IR (ATR): ꢀȬ 3012 (w), 2952 (w), 2932 (w),
2832 (w), 1607 (m), 1576 (w), 1513 (s), 1462 (s), 1440 (m), 1421 (w), 1391 (w), 1289 (m),
1244 (s), 1176 (s), 1107 (w), 1044 (m), 1026 (m), 905 (w), 850 (w), 828 (s), 812 (m), 789 (m),
779 (m), 763 (w), 734 (w), 685 (w) cmꢀ1; UVꢀvis
λmax/nm 260 (5.04) sh 290 (4.57); HRMS
(MALDI) m/z: [M]+ Calcd for C62H50O6 890.36019; Found 890.35946. Anal. calcd for
C62H50O6·H2O: C, 81.92, H, 5.77. Found: C, 81.54, H, 5.72.
2,3,6,7,12,13ꢀHexakisꢀ((3’,4’ꢀdimethoxyphenyl)triptycene 3e: According to GP1
hexabromotriptycene 1 and (3,4ꢀdimethoxyphenyl)boronic acid 2e (433 mg, 2.40 mmol, 7.0
eq.) gave after workup procedure 3e as a white powder (309 mg, 0.29 mmol, 84%): m.p.
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197 °C; H NMR (500 MHz, CDCl3): δ 7.55 (s, 6H, triptꢀH), 6.74 (d, J = 8.3 Hz, 6H, ArꢀHꢀ
4
5
6
7
8
5’), 6.71 (dd, J = 8.3, 1.6 Hz, 6H, ArꢀHꢀ6’), 6.56 (d, J = 1.6 Hz, 6H, ArꢀHꢀ2’), 5.65 (s, 2H,
13
bridgeheadꢀH), 3.84 (s, 18H, ArꢀOCH3ꢀ4’), 3.57 (s, 18H, ArꢀOCH3ꢀ3’) ppm; C NMR (126
9
MHz, CDCl3): δ 148.3 (ArCꢀOMe), 147.8 (ArCꢀOMe), 144.1 (triptC), 137.5 (triptCꢀAr),
134.4 (ArCꢀ1’), 125.9 (triptCꢀH), 122.0 (ArCꢀ6’), 113.6 (ArCꢀ2’), 110.9 (ArCꢀ5’), 56.0
(OCH3), 55.8 (OCH3), 53.3 (bridgeheadꢀC) ppm; FT IR (ATR): ꢀȬ 2991 (w), 2934 (w),
2832 (w), 1605 (w), 1578 (w), 1558 (w), 1541 (w), 1513 (s), 1464 (s), 1407 (m), 1329 (w),
1242 (s), 1170 (s), 1138 (s), 1058 (w), 1026 (s), 975 (w), 883 (m), 856 (m), 809 (m), 791 (w),
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765 (m), 734 (w), 665 (w), 610 (w) cmꢀ1; UVꢀvis
λmax/nm 265 (4.89) sh 286 (4.78); HRMS
(MALDI) m/z: [M]+ Calcd for C68H62O12 1070.42358; Found 1070.42624. Anal. calcd for
C68H62O12: C, 76.24, H, 5.83. Found: C, 75.94, H, 5.65.
2,3,6,7,12,13ꢀHexakisꢀ((3’,5’ꢀdimethoxyphenyl)triptycene 3f: According to GP1
hexabromotriptycene 1 and (3,5ꢀdimethoxyphenyl)boronic acid 2f (556 mg, 3.09 mmol, 9.0
eq.) gave after workup procedure, column chromatography on silica gel (PE/EA 2:1) and
precipitation from CHCl3 with MeOH 3f as a white powder (327 mg, 0.31 mmol, 89%): m.p.
1
345 °C (under dec.); H NMR (600 MHz, CDCl3) δ 7.55 (s, 6H, triptCꢀH), 6.30 (s, 18H, Arꢀ
Hꢀ2’,4’), 5.63 (s, 2H, bridgeheadꢀH), 3.60 (s, 36H, ArꢀOCH3ꢀ3’,5’) ppm; 13C NMR (126 MHz,
CDCl3) δ 160.3 (ArCꢀOMe), 144.3 (ArCꢀ1’), 143.5 (triptꢀC), 137.8 (triptCꢀAr), 125.8
(triptCꢀH), 108.0 (ArCꢀ2’), 99.4 (ArCꢀ4’), 55.4 (OCH3), 53.3 (bridgeheadꢀC) ppm; FT IR
(ATR): ꢀȬ 2997 (w), 2936 (w), 2834 (w), 1588 (s), 1454 (m), 1423 (m), 1391 (m), 1350 (w),
1319 (w), 1287 (w), 1250 (w), 1203 (s), 1150 (s), 1085 (w), 1060 (s), 1038 (m), 991 (w), 930
(w), 907 (w), 891 (w), 869 (w), 834 (m), 695 (m) cmꢀ1; UVꢀvis
λmax/nm 240 (5.06) sh 292
(4.43); HRMS (MALDI) m/z: [M]+ Calcd for C68H62O12 1070.42358; Found 1070.42113.
Anal. calcd for C68H62O12: C, 76.24, H, 5.83. Found: C, 76.32, H, 5.98.
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2,3,6,7,12,13ꢀHexaphenyltriptycene 3g: According to GP1 hexabromotriptycene 1 and
phenylboronic acid 2g (371 mg, 3.09 mmol, 9.0 eq.) gave after workup procedure 3g as a
1
white powder (227 mg, 0.32 mmol, 93%): m.p. >400 °C; H NMR (600 MHz, CDCl3): δ 7.55
9
(s, 6H, triptꢀH), 7.18ꢀ7.16 (m, 18H, 3’,4’,5’ꢀH), 7.10ꢀ7.09 (m, 12H, 2’,6’ꢀH), 5.65 (s, 2H,
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59
60
13
bridgeheadꢀH) ppm; C NMR (151 MHz, CDCl3): δ 144.3 (triptꢀC), 141.6 (ArCꢀ1’), 137.9
(triptCꢀAr), 130.1 (ArCꢀ2’), 128.0 (ArCꢀ3’), 126.5 (triptꢀCH), 126.2 (ArCꢀ4’), 53.3
(bridgeheadꢀC) ppm; FT IR (ATR): ꢀȬ 3081 (w), 3059 (w), 3024 (w), 2946 (w), 1601 (w),
1495 (w), 1466 (m), 1444 (w), 1395 (w), 1262 (w), 1195 (w), 1075 (w), 1020 (w), 903 (w),
805 (w), 761 (m), 695 (s), 634 (w) cmꢀ1; UVꢀvis
λmax/nm 250 (4.99) sh 289 (4.35); HRMS
(MALDI) m/z: [M]+ Calcd for C56H38 710.29680; Found 710.29800. Anal. calcd for
C56H38·1/2H2O: C, 93.43, H, 5.46. Found: C, 93.50, H, 5.52.
2,3,6,7,12,13ꢀHexakisꢀ(triptycenꢀ2’ꢀyl)triptycene 7: Analogue to GP1 hexabromotriptycene
1 (110 mg, 0.15 mmol, 1.00 eq.) and 2ꢀtriptycenylboronic acid pinacol ester 6 (379 mg, 1.00
mmol, 6.60 eq.) were mixed in 5 mL 1:1 (v/v) THF/K2CO3 (1M, aq.). Pd2dba3 (21 mg, 0.02
mmol, 0.15 eq.) and HP(tBu)3BF4 (16 mg, 0.05 mmol, 0.36 eq.) were added and heated for
the given time. After standard workup procedure followed by precipitation from hot CHCl3
with MeOH, 7 was obtained as a white powder (224 mg, 0.13 mmol, 84%): m.p. >400°C; 1H
NMR (600 MHz, CDCl3): δ 7.35 (m, 12H, Hꢀ5’,11’), 7.32 (s, 6H, triptꢀH), 7.17 (m, 12H, Hꢀ
8’,14’), 7.01 (m, 30H, Hꢀ1’, Hꢀ6’,7’,12’,13’), 6.92 (d, 6H, Hꢀ4’), 6.44 (d, 6H, Hꢀ3’), 5.40 (s,
2H, bridgeheadꢀHꢀ9,10), 5.29 (s, 6H, bridgeheadꢀHꢀ9’), 5.03 (s, 6H, bridgeheadꢀHꢀ10’) ppm;
13C NMR (151 MHz, CDCl3): δ 145.5 (Cꢀ8’a,10’a,10’b,14’a), 145.4 (Cꢀ8’a,10’a,10’b,14’a),
144.9 (Cꢀ9’a), 144.0 (triptCꢀ4a,8a,9a,10a,10b,14a), 143.4 (Cꢀ4’a), 138.3 (Cꢀ2’), 137.6 (triptCꢀ
tript’), 126.9 (Cꢀ3’), 125.9 (triptCꢀH), 125.3 (Cꢀ1’), 125.1 (Cꢀ6’,7’,12’,13’), 123.7 (Cꢀ8’,14’),
123.5 (Cꢀ5’,11’), 123.0 (Cꢀ4’), 54.1 (bridgeheadꢀCꢀ10’), 53.8 (bridgeheadꢀCꢀ9’), 53.2
(bridgeheadꢀCꢀ9,10) ppm; FT IR (ATR): ꢀȬ 3065 (w), 3038 (w), 3018 (w), 2955 (w), 1711 (w),
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1456 (s), 1417 (w), 1387 (w), 1360 (w), 1313 (w), 1295 (w), 1283 (w), 1217 (w), 1187 (w),
1158 (w), 1119 (w), 1087 (w), 1022 (w), 934 (w), 922 (w), 901 (w), 881 (w), 860 (w), 828
(w), 795 (w), 783 (w), 738 (s), 708 (w), 669 (w), 661 (w), 630 (s), 624 (s) cmꢀ1; UVꢀvis
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λ
max/nm 267 (5.28) sh 292 (4.50); MS (MALDI) m/z 1767.69 [M+H]+; Anal. calcd for
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C140H86·H2O: C, 94.14, H, 4.97. Found: C, 93.77, H, 5.10.
General procedure for Scholl oxidative cyclodehydration reactions (GP2):
In a flame dried and argon purged Schlenk flask, 1 mL MeSO3H was added dropwise to a
solution of 3aꢀc in 9 mL dry DCM and DDQ (3.3ꢀ5.0 equiv.) was added in one portion under
iceꢀbath cooling. After stirring for 5ꢀ20 minutes at 0 °C or r.t. the reaction was stopped by
pouring the dark green to blue mixture into 25ꢀ50 mL of a saturated NaHCO3 solution, which
was stirred vigorously for another 20 minutes. The organic layer was separated and the
aqueous phase extracted with DCM (2 x 15 mL). The combined organic extracts were washed
twice with water (20 mL) and brine (20 mL), dried over MgSO4 and the solvent was
evaporated under reduced pressure to give the crude product 4aꢀf as an offꢀwhite to brownish
residue.
10,21ꢀ((6’,11’ꢀDiꢀtertꢀbutyl)triphenylenꢀ2’,3’ꢀyl)ꢀ10,21ꢀdihydroꢀ(2,7,13,18ꢀtetraꢀtert
ꢀ
butyl)tetrabenzo[a,c,l,n]pentacene 4a: According to GP2 DDQ (26.2 mg, 115 µmol, 3.5 eq.)
was added to a solution of 3a (35 mg, 33 µmol, 1.0 eq.) in DCM/MeSO3H and stirred 10 min
at 0 °C. After workup the crude product was washed with nꢀhexane and nꢀpentane, to obtain
1
4a as a colourless solid (21.5 mg, 21 µmol, 62%); m.p. > 400 °C; H NMR (600 MHz,
CDCl3): δ 8.93 (s, 6H, Hꢀ1’,4’,9,11,20,22), 8.70 (d, J = 1.5 Hz, 6H, Hꢀ5’,12’,1, 8,12,19), 8.50
(d, J = 8.7 Hz, 6H, Hꢀ8’,9’,4,5,15,16), 7.66 (dd, J = 8.6, 1.5 Hz, 6H, Hꢀ7’,10’,3,6,14,17), 6.55
13
(s, 2H, bridgeheadꢀH), 1.54 (s, 54H, ꢀC(CH3)3) ppm; C NMR (151 MHz, CDCl3): δ 149.3
(Cꢀ6’,10’,2,7,13,18), 143.1 (Cꢀ2’,3’,9a,10a,20a,21a), 129.2 (Cꢀ4’b,12’a,8a,11b,19a,22b),
128.4 (Cꢀ4’a,12’b,8b,11a,19b,22a), 127.6 (Cꢀ8’a,8’b,4a,4b,15a,15b), 124.9 (Cꢀ
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7’,10’,3,6,14,17), 123.0 (Cꢀ8’,9’,4,5,15,16), 119.3 (Cꢀ5’,12’,1,8,12,19), 118.5 (Cꢀ
1’,4’,9,11,20,22), 54.3 (bridgeheadꢀC), 35.2 (C(CH3)3), 31.7 (C(CH3)3) ppm; FT IR (ATR): ꢀȬ
2953 (s), 2902 (m), 2867 (w), 1615 (w), 1493 (m), 1484 (m), 1460 (m), 1405 (m), 1362 (m),
1262 (s), 1203 (w), 1128 (w), 969 (w), 879 (m), 814 (s), 779 (w), 728 (m), 665 (w), 646 (w),
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632 (m) cmꢀ1; UVꢀvis
λmax/nm 266 (5.31), 277 (5.22), 318 (4.65) ; MS (MALDI) m/z 1041.63
[M+H]+; Anal. calcd for C80H80·H2O: C, 90.69, H, 7.80. Found: C, 90.55, H, 7.79.
10,21ꢀ((7’,10’ꢀDiꢀtertꢀbutyl)triphenylenꢀ2’,3’ꢀyl)ꢀ10,21ꢀdihydroꢀ(3,6,14,17ꢀtetraꢀtert
ꢀ
butyl)tetrabenzo[a,c,l,n]pentacene 4b: According to GP2 DDQ (26.2 mg, 115 µmol, 3.5 eq.)
was added to a solution of 3b (35 mg, 33 µmol, 1.0 eq.) in DCM/MeSO3H and stirred 12 min
at 0 °C. After workup the crude product was washed with nꢀhexane and nꢀpentane giving a
colourless solid. After precipitation from hot CHCl3/MeOH 4b was obtained as a white
1
powder (23 mg, 21 µmol, 67%); m.p. > 400 °C; H NMR (600 MHz, CDCl3) δ 8.80 (s, 6H,
Hꢀ1’,4’,9,11,20,22), 8.62 (d, J = 8.8 Hz, 6H, Hꢀ5’,12’,1,8,12,19), 8.60 (s, 6H,
Hꢀ8’,9’,4,5,15,16), 7.70 (dd, J = 8.7, 2.0 Hz, 6H, Hꢀ6’,10’,2,7,13,18), 6.15 (s, 2H,
bridgeheadꢀH), 1.49 (s, 54H, ꢀC(CH3)3) ppm; 13C NMR (151 MHz, CDCl3) δ 149.4 (Cꢀ
7’,10’,3,6,14,17), 143.0 (Cꢀ2’,3’,9a,10a,20a,21a), 129.6 (Cꢀ8’a,8’b,4a,4b,15a,15b), 127.8 (Cꢀ
4’b,12’a,8a,11b,19a,22b/4’a,12’b,8b,11a,19b,22a),
127.7
(Cꢀ4’b,12’a,8a,11b,
19a,22b/4’a,12’b,8b,11a,19b,22a), 125.0 (Cꢀ6’,10’,2,7,13,18), 123.2 (Cꢀ5’,12’,1,8,12,19),
119.0 (Cꢀ8’,9’,4,5,15,16), 118.4 (Cꢀ1’,4’,9,11,20,22), 54.5 (bridgeheadꢀC), 35.1 (C(CH3)3),
31.6 (C(CH3)3) ppm; FT IR (ATR): ꢀȬ 2961 (s), 2904 (w), 2867 (w), 1741 (w), 1717 (w), 1615
(w), 1582 (w), 1542 (w), 1513 (w), 1470 (s), 1417 (m), 1401 (m), 1362 (m), 1305 (w), 1264
(s), 1217 (w), 1203 (w), 1174 (w), 1144 (w), 1111 (w), 1042 (w), 1022 (w), 946 (w), 934 (w),
922 (w), 909 (w), 879 (s), 852 (w), 840 (w), 812 (s), 787 (w), 742 (w), 720 (w), 699 (w), 683
(w), 669 (w), 646 (w), 634 (w), 606 (s) cmꢀ1; UVꢀvis
λmax/nm 268 (5.25), 279 (5.25), 339
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(4.03), 355 (3.96); MS (MALDI) m/z 1041.64 [M+H]+; Anal. calcd for C80H80·1/3 H2O: C,
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91.78, H, 7.76. Found: C, 91.64, H, 7.58.
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10,21ꢀ(6’,11’ꢀDimethoxytriphenylenꢀ2’,3’ꢀyl)ꢀ10,21ꢀdihydroꢀ(2,7,13,18ꢀtetramethoxy)ꢀ
tetrabenzo[a,c,l,n]pentacene 4c: To a solution of 3c (29 mg, 33 µmol, 1.0 eq.) in dry DCM
(9 mL) and methanesulfonic acid (1 mL), DDQ (37 mg, 165 µmol, 5.0 eq.) was added and
stirred 10 min at 0 °C. After quenching and standard workup the crude product was washed
with nꢀhexane and nꢀpentane. Purification via column chromatography on silica gel
(toluene/ethyl acetate) gave 4c as an offꢀwhite solid (15 mg, 17 µmol, 51%); m.p. > 400 °C;
1H NMR (600 MHz, C2D2Cl4): δ 8.71 (s, 6H, Hꢀ1’,4’,9,11,20,22), 8.38 (d, J = 8.8 Hz, 6H, Hꢀ
8’,9’,4,5,15,16), 8.02 (d, J = 2.4 Hz, 6H, Hꢀ5’,12’,1,8,12,19), 7.19 (dd, J = 8.8, 2.5 Hz, 6H,
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Hꢀ7’,10’,3,6,14,17), 6.18 (s, 2H, bridgeheadꢀH), 4.02 (s, 18H, OCH3) ppm; C NMR (151
MHz, C2D2Cl4): δ 158.2 (Cꢀ6’,10’,2,7,13,18), 143.2 (Cꢀ2’,3’,9a,10a,20a,21a), 130.0 (Cꢀ
4’b,12’a,8a,11b,19a,22b), 128.0 (Cꢀ4’a,12’b,8b,11a,19b,22a), 124.6 (Cꢀ8’,9’,4,5,15,16),
124.0 (Cꢀ8’a,8’b,4a,4b,15a,15b), 118.7 (Cꢀ1’,4’,9,11,20,22), 115.8 (Cꢀ7’,10’,3,6,14,17),
106.0 (Cꢀ5’,12’,1,8,12,19), 55.8 (OCH3), 54.1 (bridgeheadꢀC) ppm; FT IR (ATR): ꢀȬ 2959 (w),
2930 (w), 2832 (w), 1711 (w), 1613 (s), 1582 (w), 1495 (s), 1462 (m), 1452 (m), 1429 (m),
1413 (s), 1299 (w), 1270 (m), 1234 (s), 1205 (m), 1174 (m), 1148 (w), 1111 (m), 1101 (m),
1046 (s), 999 (w), 973 (w), 881 (m), 850 (m), 836 (m), 801 (s), 781 (m), 716 (w), 683 (w),
622 (w) cmꢀ1; UVꢀvis
λmax/nm 272 (4.63), 321 (4.04), 348 (3.37), 367 (3.34); HRMS (MALDI)
m/z: [M]+ Calcd for C62H44O6 884.31379; Found 884.31526. Anal. calcd for
C62H44O6·2.5 H2O: C, 80.07, H, 5.31. Found: C, 79.80, H, 5.18.
10,21ꢀ(6’,7’,10’,11’ꢀTetramethoxytriphenylenꢀ2’,3’ꢀyl)ꢀ10,21ꢀdihydroꢀ
(2,3,6,7,13,14,17,18ꢀoctamethoxy)tetrabenzo[a,c,l,n]pentacene 4e: To a solution of 3e (106
mg, 99 µmol, 1.0 eq.) in dry DCM (30 mL) and methanesulfonic acid (3 mL), DDQ (74 mg,
327 µmol, 3.3 eq.) was added and stirred 10 min at 0 °C. After quenching and standard
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workup the crude product was washed with MeOH and nꢀpentane. The crude product was
further purified by recrystallization from hot CHCl3 and 4c was obtained as colorless
1
crystalline solid (51 mg, 48 µmol, 48%); m.p. > 400 °C; H NMR (300 MHz, C2D2Cl4,
9
373 K): δ 8.66 (s, 6H, Hꢀ1’,4’,9,11,20,22), 8.09 (s, 6H, Hꢀ8’,9’,4,5,15,16), 7.82 (s, 6H, Hꢀ
5’,12’,1,8,12,19), 6.17 (s, 2H, bridgeheadꢀH), 4.17 (s, 18H, OCH3ꢀ7’,10’,3,6,14,17), 4.08 (s,
18H, OCH3ꢀ6’,11’,2,7,13,18) ppm; 13C NMR (75 MHz, C2D2Cl4, 373 K): δ 150.0
(Cꢀ7’,10’,3,6,14,17), 149.6 (Cꢀ6’,11’,2,7,13,18), 142.4 (Cꢀ2’,3’,9a,10a,20a,21a), 126.9
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(Cꢀ4’a,12’b,8b,11a,19b,22a),
124.4
(Cꢀ8’a,8’b,4a,4b,15a,15b),
123.9
(Cꢀ4’b,12’a,8a,11b,19a,22b), 117.7 (Cꢀ1’,4’,9,11,20,22), 106.7 (Cꢀ8’,9’,4,5,15,16) , 106.1
(Cꢀ5’,12’,1,8,12,19), 56.7 (OCH3), 56.5 (OCH3), 54.3 (bridgeheadꢀC) ppm; FT IR (ATR): ꢀȬ
2993 (w), 2932 (w), 2826 (w), 1739 (w), 1713 (w), 1617 (m), 1509 (s), 1493 (m), 1462 (m),
1448 (m), 1415 (s), 1382 (w), 1333 (w), 1258 (s), 1211 (s), 1197 (s), 1170 (m), 1148 (s),
1036 (s), 975 (w), 956 (w), 899 (w), 875 (w), 838 (s), 816 (m), 789 (w), 765 (m), 722 (w),
683 (w), 618 (s) cmꢀ1; UVꢀvis
λmax/nm 283 (5.30), 314 (4.95), 327 (4.94) sh 347 (4.22);
HRMS (MALDI) m/z: [M]+ Calcd for C68H56O12 1064.37663; Found 1064.37334. Anal. calcd
for C68H56O12·1.5 H2O: C, 74.78, H, 5.45. Found: C, 74.85, H, 5.51.
10,21ꢀ[6’,7’,10’,11’ꢀDi(9’’,10’’ꢀdihydroanthracenꢀ9’’,10’’ꢀyl)triphenylenꢀ2’,3’ꢀyl]ꢀ10,21ꢀ
dihydroꢀ(2,3,6,7,13,14,17,18ꢀtetra(9’’,10’’ꢀdihydroanthracenꢀ9’’,10’’ꢀ
yl)tetrabenzo[a,c,l,n]pentacene 8: To a solution of 7 (30 mg, 17 µmol, 1.0 eq.) in dry DCM
(9 mL) and methanesulfonic acid (1 mL), DDQ (13.5 mg, 59 µmol, 3.5 eq.) was added and
stirred 15 min at 0 °C. After quenching and standard workup the crude product was washed
with nꢀhexane and nꢀpentane giving a colourless solid (22 mg, 13 µmol, 74%); m.p. > 400 °C;
1H NMR (600 MHz, CDCl3) δ 8.69 (s, 6H, Hꢀ1’,4’,9,11,20,22), 8.58 (s, 6H, Hꢀ
5’,12’,1,8,12,19), 8.50 (s, 6H, Hꢀ8’,9’,4,5,15,16), 7.47 – 7.42 (m, 24H, Hꢀ1’’,4’’,5’’,8’’), 7.03
– 6.98 (m, 24H, Hꢀ2’’,3’’,6’’,7’’H), 6.04 (s, 2H, core bridgeheadꢀHꢀ10,21), 5.62 (s, 6H,
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bridgeheadꢀHꢀ9’’), 5.59 (s, 6H, bridgeheadꢀHꢀ10’’) ppm; 13C NMR (151 MHz, CDCl3)
δ 145.1 (Cꢀ4’’a,8’’a,9’’a,10’’a), 143.2 (Cꢀ6’,11’,2,7,13,18/7’,10’,3,6,14,17), 143.2 (Cꢀ
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6’,11’,2,7,13,18/7’,10’,3,6,14,17),
142.6
(Cꢀ2’,3’,9a,10a,20a,21a),
127.8
(Cꢀ
9
4’a,12’b,8b,11a,19b,22a), 127.5 (Cꢀ4’b,12’a,8a,11b,19a,22b/8’a,8’b,4a,4b,15a,15b), 127.4
(Cꢀ4’b,12’a,8a,11b,19a,22b/8’a,8’b,4a,4b,15a,15b), 125.5 (Cꢀ2’’,3’’,6’’,7’’), 123.9 (Cꢀ
1’’,4’’,5’’,8’’), 118.2 (Cꢀ1’,4’,9,11,20,22), 118.0 (Cꢀ5’,12’,1,8,12,19), 118.0 (Cꢀ
8’,9’,4,5,15,16), 54.4 (core bridgehead Cꢀ10,21), 54.4 (bridgehead Cꢀ9’’), 54.3 (bridgehead
Cꢀ10’’) ppm; FT IR (ATR): ꢀȬ 3067 (w), 3040 (w), 3020 (w), 2953 (w), 2924 (w), 1737 (w),
1711 (w), 1680 (w), 1588 (w), 1472 (w), 1458 (m), 1423 (m), 1376 (w), 1338 (w), 1295 (w),
1260 (w), 1203 (w), 1189 (w), 1164 (w), 1156 (w), 1093 (w), 1024 (w), 1001 (w), 973 (w),
934 (w), 920 (w), 881 (m), 797 (w), 740 (s), 689 (w), 669 (w), 634 (m), 626 (s) cmꢀ1; UVꢀvis
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λ
max/nm 282 (5.29), 312 (4.99), 323 (4.96) sh 345 (4.40); MS (MALDI) m/z 1761.64 [M+H]+;
Anal. calcd for C140H80·2H2O: C, 93.51, H, 4.71. Found: C, 93.48, H, 4.70.
Acknowledgement
The authors would like to thank ‘Deutsche Forschungsgemeinschaft’ and ‘Fonds der
Chemischen Industrie’ for financial support. We would like to thank Michael Ganschow for
preliminary experiments.
Supporting Information
1
The Supporting Information contains H, 13C and 2D NMRꢀspectra of all new compounds
(3aꢀ3g, 4aꢀ4c, 4e, 5ꢀ8). Furthermore single crystal Xꢀray diffraction data (and cifꢀfiles) of 3a,
3b and 4e have been provided. This material is available free of charge via the Internet at
http://pubs.acs.org/.
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