Direct arylation of oligonaphthalenes using PIFA/BF3· Et2O: From double arylation to larger oligoarene products

Article abstract of DOI:10.1021/jo401001k

Direct dehydrogenative coupling between the linear ter- and quaternaphthalenes and substituted benzenes was achieved under the Kita conditions using the hypervalent PIFA/BF₃ reagent. Products resulting from either the double arylation of the naphthalenic substrate or the formal dimerizative arylation have been prepared. For example, in the latter mode, ternaphthalene was converted into a series of linear octiarenes (counting the capping Ar). The process represents an alternative to the cross-coupling methodologies employed in related syntheses and proceeds via a selective functionalization of six relatively inert aromatic CH bonds.

Full text of DOI:10.1021/jo401001k

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Note
Direct Arylation of Oligonaphthalenes Using PIFA/BF3•Et2O:
From Double Arylation to Larger Oligoarene Products
Wusheng Guo, Enrico Faggi, Rosa María Sebastián, Adelina Vallribera, Roser Pleixats, and Alexandr Shafir
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/jo401001k • Publication Date (Web): 16 Jul 2013
Downloaded from http://pubs.acs.org on July 19, 2013
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Direct Arylation of Oligonaphthalenes Using PIFA/BF3·Et2O: From
Double Arylation to Larger Oligoarene Products.
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Wusheng Guo, Enrico Faggi, Rosa M. Sebastián, Adelina Vallribera,* Roser Pleixats*
and Alexandr Shafir*
Department of Chemistry, Universitat Autònoma de Barcelona, 08193ꢀCerdanyola del Vallès, Barcelona
(Spain)
*Eꢀmails: roser.pleixats@uab.cat, adelina.vallribera@uab.cat, alexandr.shafir@uab.cat
Abstract. Direct dehydrogenative coupling between the linear terꢀ and quaternaphthalenes and
substituted benzenes was achieved under the Kita conditions using the hypervalent PIFAꢀBF3 reagent.
Products resulting from either the double arylation of the naphthalenic substrate or the formal
dimerizative arylation have been prepared. For example, in the latter mode, ternaphthalene was converted
into a series of linear octiꢀarenes (counting the capping Ar). The process represents an alternative to the
crossꢀcoupling methodologies employed in related syntheses, and proceeds via
functionalization of six relatively inert aromatic CH bonds.
a selective
=======================================================================
The carbon—carbon coupling between arenes via the transformation of the CH groups is a
particularly promising goal within the overall challenge of the CH bond functionalization. In
this field, the earlier stoichiometric methods,1ꢀ3 many in the form of the Scholl reaction, have
recently been complemented by the development of the catalytic dehydrogenative coupling
processes.4, 5 The challenge of finding a practical procedure applicable to a particular substrate
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lies both in the relative inertness of a CH bond, and in our ability to direct the reaction towards a
specific CH site. In an intermolecular system, the discrimination can be achieved through the
use of an appropriate directing group,6 or by employing a substrate with an inherently reactive
CH position7ꢀ9 in certain types of radical and electrophilic reactions.
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This latter reactivity manifold was nicely illustrated by Kita and coꢀworkers in an arylation of
naphthalene with polyalkylbenzenes (e.g. mesitylene) using a combination of phenyliodine
bis(trifluoroacetate), PIFA, and BF3ꢁEt2O (Scheme 1, A).10 For this system, the arylation took
place exclusively at the α position of naphthalene, and the method complemented the existing
metalꢀcatalyzed crossꢀcoupling protocols; the method was also extended to the direct coupling
12
of heteroarenes.11,
Our group later showed that the outcome in the case of the
naphthalene/mesitylene pair was highly dependent on the PIFAꢀnaphthalene ratio. Thus,
mesitylnaphthalene 1a was the main product at a ratio of 1:1, while the arylated binaphthalene
2a formed predominantly (45%) when this ratio was raised to ~2:1 (Scheme 1A);13 in both
cases, the reaction was accompanied by the formation of small amounts of oligonaphthalenes
Mesꢀ(nap)3ꢀMes (3a), Mesꢀ(nap)4ꢀMes (4a), and longer oligomers, appearing as trailing
fluorescent spots on a TLC plate (Figure 1A). Such products would be consistent with further
oxidative coupling of the initially formed 1a either through dimerization, or by reacting with
extra equivalents of naphthalene prior to a second arylation with mesitylene. We also found that
when a naphthalene was replaced with 1,1’ꢀbinaphthalene (Nap2), the corresponding coupling
of four arene molecules (2 Nap2 and 2 ArH) became the predominant process, giving the
diarylated tetranaphthalene 4a in 87% (Scheme 1B).13
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Scheme 1. Previous results on oxidative arylation of naphthalenes using PIFA/BF3.
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The TLC traces of the reaction mixtures for the arylation of naphthalene and 1,1’ꢀ
binaphthalene (Figure 1) provides a nice visual comparison for the two outcomes. As mentioned
above, arylation of naphthalene yields, in addition to 1a, oligonaphthalenes (2a, 3a, 4a, etc.)
capped on both sides by a mesityl (trace A). Under the same conditions, 1,1’ꢀbinaphthalene is
expected to give an analogous mixture devoid of the nꢀodd components (trace B). Indeed, while
the nꢀeven 2a and 4a are found on both traces, product 3a is absent in trace B.
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Mes
A
B
1a
n
2a
Mes
Mes
n=2
n=3
n=4
3a
Mes
Mes
n=5
n=6
Mes
Mes
4a
Figure 1. TLC traces for the coupling of mesitylene with: A) naphthalene, and B) 1,1´ꢀ
binaphthalene.
Control experiments showed that in the case of the 1,1’ꢀbinaphthalene the process likely
begins with the formation of the monoarylated product, which then dimerizes. We showed,
however, that alternative paths may also be operational. Thus, the coupling between the
monoarylated product with a second binaphthalene may be followed by the second arylation;
finally, dimerization of 1,1’ꢀbinaphthalene followed by a double arylation was also shown to be
feasable.13 In fact, these experiments and the surprisingly overall high efficiency for this formal
dimerizative arylation process suggested that the use of longer chain oligonaphthalenes, such as
terꢀ and quaterꢀnaphthalenes might also be feasible.14 To this end, we developed the synthesis of
the parent linear Nap3 and Nap4 through a twoꢀstep procedure involving selective
dibromination15, 16 followed by SuzukiꢀMiyaura coupling with the 1ꢀnaphthaleneboronic acid
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(Scheme 2, see Supporting Info). Even for the simple trinaphthalene Nap3, the fairly complex
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13C NMR spectrum consisting of a large number of the somewhat broadened peaks,17,
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suggested that the product exists as a mixture of the slowly interconverting atropisomeric
aRaR/aSaS (rac, C2) and aRaS (meso σ) forms. The procedure afforded multigram quantities of
Nap3 and Nap4 in respective 77% and 93% yields over the two steps.19
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Scheme 2. Preparation of substrates Nap3 and Nap4.
As was the case for the parent 1,1’ꢀbinaphthalene, the next higher homologue, Nap3, could be
envisaged undergoing, in addition to the monarylation, a double arylation to 3 (Table 1, path I),
or a formal dimerizative arylation to give the linear sexinaphthalene 6 (path II).
Thus, the reactivity of Nap3 with mesitylene was examined under the conditions similar to
those used for the binaphthalene. The test revealed that, unlike for Nap2, the simple double
arylation path I is somewhat preferred for Nap3. Specifically, the addition of the PIFA/BF3
reagent (0.6 mmol/1.2 mmol) to a mixture of Nap3 (0.3 mmol) and mesitylene (1.2 mmols) led
to a 90% yield of 3a, a compound previously identified (see Figure 1) as a minor fraction in the
arylation of naphthalene (Table 1, entry 1). The reactivity difference between Nap2 and Nap3 in
the Kitaꢀtype arylation is noteworthy. Assuming the monoarylation as the first step, the
preference for arylative dimerization in Nap2 and for selective diarylation in Nap3 indicates a
significantly more favoured second arylation in the latter.
As previously documented for 2a,13 two singlets are observed in the 1H NMR spectrum of 3a
due to the diastereotopic ortho Me resonances within each mesityl; signal doubling is also
observed for the aromatic mꢀH. A diastereotopic relationship between the two halves of the
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“hindered” mesityl group is a consequence of their disposition over the two diastereotopic faces
of the adjacent naphthalene (Figure 2).20
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o-Me
o-Me
p-Me
m-H
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Figure 2. Different chemical environments for the two halves of the mesitylene and the
resulting doubling of the 1H pattern.
A good yield of the double arylation product was also obtained using pentamethylbenzene
(Table 1, entry 2, 89%), and triethylbenzene (entry 3, 71%). In contrast, the use of bulkier
arenes drastically lowered the efficiency of the double arylation, and only a modest 33% of 3d
was isolated using 1ꢀtertꢀbutylꢀ3,5ꢀdimethylbenzene (entry 4). Similarly, the use of 2,4,6ꢀ
trimethylꢀ1,1'ꢀbiphenyl gave 3e in 32% yield (entry 5). In the latter two cases, however, the
decrease in the yield of 3 was compensated by the appearance of nonꢀnegligible quantities of the
octiꢀarene products 6d (31%, entry 4) and 6e (22%, entry 5). An approx. 1:1 mixture of 3f:6f
was also obtained using 1,2,4,5ꢀtetramethylbenzene (entry 6).
Table 1. Oxidative arylation of Nap3 using PIFA/BF3ꢁEt2O. a,b
Entry
Ar-H
1
3a
3b
3c
3d
90
89
71
33
6a
6b
6c
6d
ꢀꢀ
ꢀꢀ
2
3
4
<5%
31
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3e
3f
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6e
6f
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aUsing ternaphthalene 0.3 mmol Nap3, 1.2 mmol of PIFA and 1.2 mmol BF3ꢁEt2O in CH2Cl2 at ꢀ78 oC. bYields of
isolated products.
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The formation, albeit in modest yields, of 6dꢀ6f, represents an assembly of a linear octiarene
(counting the capping arenes) using simple aromatic building blocks, whereby three new CꢀC
bonds have been formed in the process from six unactivated arene molecules. The new products
appear at Rf lower than those of the corresponding 3dꢀ3f. The identity of the new oligoarenes
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was confirmed, in addition to the H and 13C NMR spectra, via high resolution MALDI TOF
spectrometry.
Given that the product distribution in the arylation of Nap2 was dependent on the amount of
PIFA, we looked for a similar influence for Nap3. Taking as a model the coupling between 1ꢀ
tertꢀbutylꢀ3,5ꢀdimethylbenzene (entry 4, Table 1) and Nap3 (ratio 4:1), the yields of the simple
and formal dimerizative arylation products 3d and 6d were determined as a function of the
equivalents of PIFA employed (Figure 3, A).21 Thus, both yields grew steadily with increasing
amounts of PIFA, with the 6d reaching a maximum yield (32%) at 2 equiv. In turn, the yield of
3d reached its maximum (40%) with 3 equiv. of PIFA (at the expense of 6d); further increase in
the PIFA loading was found to be detrimental. In a separate experiment, the yields of both 3d
and 6d were found to peak at ~4ꢀ5 equiv of ArH added, with 3d slightly favoured (as expected)
at higher ratios of ArH (Figure 3, B).
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0
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0
A
B
0
2
4
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0
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PIFA (equiv)*
ArH (equiv)*
tBu
tBu
tBu
3d
6d
tBu
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Figure 3. Yields of 3d and 6d, (% by HPLC, corrected) as a function of the amount of PIFA (A)
and ArH (B) used. * equiv PIFA = mmol(PIFA)/mmol(Nap3).
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Finally, the oxidative arylation of the next higher homologue Nap4 was explored (Scheme 3,
Figure 4). Previously,13 we showed that the arylation of this substrate with mesitylene gave
predominantly the doubly arylated product 4a, indicating the substrate’s decreased ability to
undergo the formation of the larger formally dimeric products.
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Ar-H
PIFA
BF3·Et2O
4
8
CH2Cl2
Ar
Ar
Ar
+
Ar
4
4
Scheme 3. Oxidative arylation of Nap4 using PIFAꢀBF3•Et2O.
Expanding on that preliminary result, and after some optimization, we found that in addition
to the 91% yield obtained for 4a, good yields were reached for the pentamethylphenyl and
triethylphenyl derivatives, 4b (95%) and 4c (77%), respectively. Once again, arylation using the
bulkier 1ꢀtertꢀbutylꢀ3,5ꢀdimethylbenzene and 2,4,6ꢀtrimethylꢀ1,1'ꢀbiphenyl gave moderate
yields of the corresponding products 4d (52%) and 4e (60%), respectively. In the case of
1,2,4,5ꢀtetramethylbenzene, only a 37% yield of the double arylation product 4f was obtained.
This low yield was attributed to the further oxidative coupling at the pꢀH at the
tetramethylphenyl unit of the newly formed 4f, leading to an intractable oligomer.
Figure 4. Products obtained via oxidative arylation of Nap4 using PIFA with BF3•Et2O.
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Unlike in the case of Nap3, however, the use of Nap4 as substrate did not afford any
significant quantities of the larger oligoarene 8 (i.e. Arꢀnap8ꢀAr). Nevertheless, small amounts
of 8 were indeed detected in some cases. For example, the TLC analysis in the reaction mixture
using 1,2,4,4ꢀtetramethylbenzene as substrate showed the principal leading fraction (product 4d)
trailed by a minor component, consistent with the presence of a larger oligomer. Repeated
purification of this fraction by preparative TLC afforded small quantities of the deciꢀarene 8f,
whose identity was confirmed by the observation of a peak at 1274.5852 in the high resolution
MALDIꢀTOF analysis (see Support. Info).
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In summary, the Kitaꢀtype direct dehydrogenative arylation protocol using the BF3ꢀactivated
phenyliodine bis(trifluoroacetate) (PIFA) has now been successfully applied to the arylation of
the linear terꢀ and quaternaphthalenes. In contrast to the reactions using naphthalene and
binaphthalene, the arylation of oligonaphthalenes has led predominantly to the doubleꢀarylation
products 3 and 4. Still, moderate yields of the larger multiꢀarene 6 could be obtained in some
cases for Nap3. Such synthesis of an octiꢀarene is remarkable, in that it constitutes a direct
oxidative metalꢀfree assembly of four unfunctionalized building block molecules. The interest
in practical syntheses of such large oligonaphthalenes lie in their optoelectronic properties
relevant in the design of solar cells or OLED devices.22 Finally, small quantities of the formal
dimerizative arylation product 8d and 8f have also been detected (4% isolated yield for 8f),
representing the oneꢀpot assembly of a linear deciꢀarene.
EXPERIMENTAL SECTION
General. All reagents were purchased from commercial sources and used as received. 1,4ꢀ
Dibromonaphthalene was prepared following a reported procedure;23 2ꢀphenylmesitylene was prepared
following a Suzuki coupling protocol as previously described;13 4,4’ꢀdibromoꢀ1,1’ꢀbinaphthalene was
prepared as already described.24 Dichloromethane was dried by passing through a column of activated
1
molecular sieves. Silica gel usec corresponds to 230ꢀ440 mesh. Routine H and 13C NMR spectra were
1
recorded on 250 and 360 MHz instruments. H NMR chemical shifts are given relative to the residual
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protio signal of CDCl3 (7.26 ppm). 13C NMR spectra are given relative to the 13C resonance of CDCl3
(77.16 ppm). High resolution MALDIꢀTOF spectra were recorded using dithranol as the matrix and
polyethylene glycol as internal reference. IR data were obtained using a spectrometer equipped with an
ATR probe. The yields of compound 3d and 6d related to conditions optimization were determined by
HPLC, using a column packed with diphenyl silica as stationary phase (Pursuit XRs Diphenyl from
Agilent Technologies) and a mixture of hexane/acetonitrile/isopropanol (10/20/70) as a mobile phase with
a flow rate of 0.6 mL/min. For all the analyses, 1,1’ꢀbinaphthalene was used as internal standard.
Synthesis and Characterization Details.
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1,4-dibromonaphthalene.23
A stirred solution of naphthalene (8.970 g, 69.692 mmol) in
dichloromethane (70 mL) was cooled to ꢀ30 °C and then bromine (33.600 g, 10.8 mL, 210 mmol) was
added dropwise over 10 min in the dark while maintaining the temperature at ꢀ30 °C with constant
magnetic stirring. The mixture was then stirred for 20 h in the dark at ꢀ25 °C. At this point, the excess of
bromine was quenched with an aqueous solution of NaHSO3. The organic layer was separated and further
washed with aqueous solutions of NaHSO3 and NaOH (2M). The organic layer was dried over anhydrous
Na2SO4, and concentrated to dryness to afford the crude compound, which was further purified by silica
gel chromatography using hexane as eluent. White powder, yield: 17.000 g, 85%; mp 79ꢀ81 °C; lit23. 80ꢀ
82 °C; 1H NMR (360 MHz, CDCl3): δ 8.25 (dd, J = 6.5, 3.3 Hz, 2H), 7.65 (dd, J = 6.4, 3.3 Hz, 2H), 7.63
(s, 2H) ppm. 13C{1H} NMR (90 MHz, CDCl3): δ 133.1, 130.2, 128.3, 127.9, 122.7 ppm; IR (ATR) ν (cmꢀ
1): 3067, 1583, 1492, 1365, 1251, 959, 812, 749.
4,4’-dibromo-1,1’-binaphthalene.13, 24 A stirred solution of 1,1’ꢀbinaphthalene (3.050 g, 11.993 mmol)
in chloroform (96 mL) was cooled to 0 °C. Bromine (9.010 g, 2.9 mL, 56.383 mmol) was added dropwise
over 10 min in the dark while maintaining the temperature at 0 °C and with a steady magnetic stirring.
The mixture was stirred for 4 h in the dark at 0 °C. At this point, aqueous NaHSO3 solution was added to
quench the excess of bromine. The organic layer was separated and washed successively with aqueous
NaHSO3 solution, aqueous NaOH solution (2 M) and water. The organic layer was dried over anhydrous
Na2SO4, and concentrated to dryness to afford the crude compound, which was recrystallized from
1
boiling chloroform. White needle crystals, 4.600 g, yield: 94 %; mp 214ꢀ216 °C; lit.24 215ꢀ217 °C;. H
NMR (360 MHz, CDCl3): δ 8.37 (d, J = 8.6 Hz, 2H), 7.90 (d, J = 8.6 Hz, 2H), 7.62ꢀ7.58 (m, 2H), 7.35ꢀ
7.31 (m, 6H); 13C{1H} NMR (90 MHz, CDCl3): δ 137.8, 134.0, 132.1, 129.6, 128.3, 127.6, 127.1, 123.1
ppm; IR (ATR) ν (cmꢀ1): 3071, 1582, 1450, 1366, 1248, 954, 817, 754.
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1,1’:4’,1’’–ternaphthalene (Nap3). To a mixture of 1,4ꢀdibromonaphthalene (2.000 g, 6.994 mmol),
naphthaleneꢀ1ꢀboronic acid (3.610 g, 20.990 mmol), Pd(OAc)2 (94 mg, 0.419 mmol), PPh3 (0.330 g,
1.258 mmol), and Na2CO3 (2.230 g, 21.038 mmol) were added H2O (14 mL), THF (53 mL) and toluene
(140 mL) and the resulting suspension was heated to reflux for 22 hours. The reaction mixture was then
cooled to room temperature and the solvent was evaporated. The crude product was purified by column
chromatography (silica gel, hexane:AcOEt 20:1; Rf = 0.43) affording 1,1’:4’,1’’ꢀternaphthalene. Cottonꢀ
like white solid, yield: 2.400 g, 90%; mp 188ꢀ190 °C; 1H NMR (250 MHz, CDCl3): δ 8.00ꢀ7.97 (m, 4H),
7.68ꢀ7.48 (m, 12H), 7.43ꢀ7.35 (m, 2H), 7.29ꢀ7.26 (m, 2H); 13C{1H} NMR (90 MHz, CDCl3): δ 138.7,
138.5, 138.4, 133.7, 133.10, 133.07, 133.0, 128.37, 128.33, 128.1, 127.5, 127.0, 126.8, 126.23, 126.18,
126.03, 126.00, 126.96, 125.6. HRMS (MALDIꢀTOF) m/z calcd for C30H20 [M]+:380.1554, found:
380.1569; IR (ATR) ν (cmꢀ1): 3043, 1571, 1505, 1375, 1256, 776, 758..
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1,1’:4’,1’’:4’’,1’’’- quaternaphthalene (Nap4).13 To a mixture of 1, 4ꢀdibromonaphthalene (2.470 g,
5.993 mmol), naphthaleneꢀ1ꢀboronic acid (2.890 g, 16.803 mmol), Pd(OAc)2 (135 mg, 0.601 mmol),
PPh3 (488 mg, 1.861 mmol), and Na2CO3 (1.910 g, 18.019 mmol), were added of H2O (9 mL), THF (36
mL) and toluene (108 mL) and the resulting suspension was heated to reflux for 24 hours, at which point
all of the aryl halide has been consumed as gauged by GC. The reaction mixture was cooled to room
temperature and the solvent was evaporated to dryness. The crude product was purified by column
chromatography (silica gel, neat hexane; Rf = 0.1). Cottonꢀlike white solid, yield: 3.000 g, 99%; mp 178ꢀ
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181 °C; H NMR (250 MHz, CDCl3): δ 8.01ꢀ7.99 (m, 4H), 7.77ꢀ7.49 (m, 16H), 7.45ꢀ7.32 (m, 6H);
13C{1H} NMR (90 MHz, CDCl3): δ 138.7, 138.6, 138.5, 133.7, 133.13, 133.09, 128.40, 128.36, 128.2,
127.7, 127.6, 127.1, 126.8, 126.3, 126.2, 126.1, 125.6 ppm; HRMS (MALDIꢀTOF) m/z calcd for C40H26
[M]+: 506.2029, found: 506.2019; IR (ATR) ν (cmꢀ1): 3041, 1592, 1506, 1373, 1256, 800, 761.
General Procedure for the Oxidative Arylation. To a solution of 1,1’:4’,1’’ꢀternaphthalene, Nap3, or
1,1’:4’,1’’:4’’,1’’’ꢀ quaternaphthalene, Nap4, (0.300 mmol) and the chosen arene (1.200 mmol) in dry
dichloromethane (2 mL) at ꢀ78 ºC and under nitrogen atmosphere, were added BF3•Et2O (170 mg, 150 ꢂL,
1.200 mmol) and a solution of PIFA (258 mg, 0.600 mmol) in dichloromethane (anhydrous, 2 mL). The
resulting deep purple reaction mixture was kept below ꢀ50 ºC for 3 hours and then was allowed to warm
up to room temperature for addition 20 hours. The mixture was quenched with saturated aqueous
NaHCO3 (5 mL) and was transferred to a separatory funnel. The organic layer was separated and the
aqueous phase was extracted with dichloromethane (2 x 20 mL). The combined organic fraction was
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dried over anhydrous Na2SO4 and concentrated to dryness. The crude product was purified by flash
chromatography. Given the difficult separation due to similar Rf values for the major and the minor, a
second or even a third purification by flash chromatography were performed when needed. In some cases,
preparatory paper TLC was used to obtain samples suitable for analysis.
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4, 4’’-Dimesityl-1,1’:4’,1’’-ternaphthalene (3a). Following the general procedure, ternaphthalene,
Nap3 (150 mg, 0.394 mmol) was allowed to react with 1,3,5ꢀtrimethylbenzene (230 ꢂL, 0.846 g/mL,
1.610 mmol). Column chromatography: silica gel, hexane:AcOEt 70:1, Rf = 0.25. Light yellow powder,
223 mg, yield: 90%; mp 212ꢀ214 °C; 1H NMR (360 MHz, CDCl3): δ 7.72 ꢀ 7.59 (m, 8H), 7.52 ꢀ 7.44 (m,
2H), 7.41 ꢀ 7.33 (m, 8H), 7.10ꢀ7.09 (two overlapping s, 2H + 2H), 2.45 (s, 6H), 2.07 (s, 6H), 2.03 (s, 6H);
13C{1H} NMR (90 MHz, CDCl3): δ 138.9, 138.6, 137.7, 137.2, 137.1, 137.0, 133.42, 133.36, 133.3, 133.2,
132.1, 128.3, 128.0, 127.7, 127.2, 127.0, 126.5, 126.0, 125.6, 21.3, 20.7 ppm. HRMS (MALDIꢀTOF) m/z
calcd for C48H40 [M]+: 616.3124, found: 616.3125; IR (ATR) ν (cmꢀ1): 3038, 2919, 2854, 1374, 1260, 844,
762.
4, 4''-Bis(2,3,4,5,6-pentamethylphenyl)-1,1':4',1''-ternaphthalene (3b). Following the general
procedure, ternaphthalene (114 mg, 0.300 mmol) was allowed to react with 2,3,4,5,6ꢀpentamethylbenzene
(178 mg, 1.201 mmol). Column chromatography: silica gel, hexane:AcOEt 70:1, Rf = 0.16. Light yellow
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powder, 180 mg, yield: 89%; mp 198ꢀ201 °C; H NMR (360 MHz, CDCl3): δ 7.73 ꢀ 7.62 (m, 8H), 7.56 ꢀ
7.52 (m, 2H), 7.46 ꢀ 7.34 (m, 8H), 2.42 (s, 6H), 2.37 ꢀ 2.36 (two overlapping s, 6H + 6H), 2.01 (s, 6H),
1.96 (s, 6H); 13C{1H} NMR (90 MHz, CDCl3): δ 140.9, 138.7, 138.6, 137.6, 137.55, 137.45, 134.4, 133.2,
132.73, 132.70, 132.65, 132.56, 128.0, 127.7, 127.1, 126.70, 126.67, 126.6, 126.0, 125.9, 18.6, 18.5, 17.1,
16.9 ppm. HRMS (MALDIꢀTOF) m/z calcd for C52H48 [M]+: 672.3751, found: 672.3752; IR (ATR) ν
(cmꢀ1): 3040, 2990, 2916, 1372, 906, 761, 731.
4, 4''-bis(2,4,6-triethylphenyl)-1,1':4',1''-ternaphthalene (3c). Following the general procedure,
ternaphthalene (114 mg, 0.300 mmol) was allowed to react with 1,3,5ꢀtriethylbenzene (226 ꢂL, 0.862
g/mL, 1.200 mmol). Column chromatography: silica gel, hexane : AcOEt gradient from 250:1 to 100:1
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(Rf = 0.09). Light brown powder, 150 mg, yield: 71%; mp 135ꢀ138 °C; H NMR (360 MHz, CDCl3): δ
7.74 ꢀ 7.62 (m, 8H), 7.50 ꢀ 7.47 (m, 4H), 7.37 – 7.35 (m, 6H), 7.14 (two overlapping s, 2H + 2H), 2.82 –
2.76 (q, 4H, J = 7.4 Hz), 2.39 – 2.29 (m, 8H), 1.41 – 1.37 (t, 6H, J = 7.6 Hz), 1.11 – 1.03 (m, 12 H);
13C{1H} NMR (90 MHz, CDCl3): δ 143.7, 143.2, 143.1, 138.3, 137.7, 136.0, 133.20, 133.18, 133.0, 127.8,
127.7, 127.12, 127.05, 126.0, 125.94, 125.91, 125.32, 125.29, 29.0, 27.02, 26.95, 15.9, 15.8, 15.7 ppm.
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HRMS (MALDIꢀTOF) m/z calcd for C54H52 [M]+: 700.4064, found: 700.4078; IR (ATR) ν (cmꢀ1): 3044,
2967, 2933, 2873, 1570, 1460, 1375, 840, 764.
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4, 4''-bis(4-(tert-butyl)-2,6-dimethylphenyl)-1,1':4',1''-ternaphthalene (3d). Following the general
procedure, ternaphthalene (114 mg, 0.300 mmol) was allowed to react with 5ꢀtertꢀbutylꢀmꢀxylene (195
mg, 225 ꢂL, 1.200 mmol). Column chromatography: silica gel, hexane:AcOEt gradient from 250:1 to
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100:1 (Rf = 0.21). Light yellow powder, 70 mg, yield: 33%; mp > 300 °C; H NMR (CDCl3): δ 7.72 –
7.58 (m, 8H), 7.52 ꢀ 7.44 (m, 4H), 7.40 ꢀ 7.33 (m, 6H), 7.25 (two overlapping s, 2H + 2H), 2.09 (s, 6H),
2.05 (s, 6H), 1.44 (s, 18H). 13C{1H} NMR (90 MHz, CDCl3): δ 150.2, 139.1, 138.64, 138.58, 137.6,
136.9, 136.7, 133.3, 132.2, 128.0, 127.7, 127.2, 127.1, 126.4, 126.1, 126.0, 124.5, 34.6, 31.7, 21.1 ppm.
HRMS (MALDIꢀTOF) m/z calcd for C54H52 [M]+: 700.4064, found: 700.4068; IR (ATR) ν (cmꢀ1): 3040,
2952, 2864, 1456, 1375, 841, 763.
4,4’’’’’-Bis(4-tert-butyl-2,6-dimethylphenyl)-1,1':4',1'':4’’,1’’’:4’’’,1’’’’:4’’’’,1’’’’’-
sexinaphthalene (6d). From the same experiment used to obtained 3d, an additional product was isolated
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that corresponded to the hexanaphthalene 6d. Light brown powder, 50 mg, yield: 31%. H NMR (360
MHz, CDCl3): δ 7.87 ꢀ 7.65 (m, 20H), 7.56 ꢀ 7.54 (m, 2H), 7.52 ꢀ 7.39 (m, 14H), 7.29 (two overlapping s,
2H + 2H), 2.14 – 2.09 (two s, 6H + 6H), 1.47 (s, 18H). 13C{1H} NMR (90 MHz, CDCl3): δ 150.2, 139.1,
138.6, 137.6, 136.9, 136.7, 133.4, 133.2, 132.3, 128.0, 127.8, 127.2, 126.4, 126.1, 126.02, 125.97, 124.5,
34.6, 31.7, 21.1 ppm. HRMS (MALDIꢀTOF) m/z calcd for C84H70 [M]+: 1078.5472, found: 1078.5488; IR
(ATR) ν (cmꢀ1): 3039, 2951, 1509, 1372, 837, 760.
4, 4''-Bis(2,4,6-trimethyl-[1,1'-biphenyl]-3-yl)-1,1':4',1''-ternaphthalene (3e). Following the general
procedure, ternaphthalene (114 mg, 0.300 mmol) was allowed to react with 2ꢀphenylmesitylene (235 mg,
1.200 mmol). Column chromatography: silica gel, hexane:AcOEt 70:1 (Rf = 0.15). Orange powder, 74
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mg, yield: 32%; mp 209ꢀ212 °C; H NMR (360 MHz, CDCl3): δ 7.73 ꢀ 7.60 (m, 10H), 7.49 ꢀ 7.28 (m,
18H), 7.21 and 7.20 (two overlapping s, 1H + 1H), 2.16 (s, 6H), 2.11 (s, 3H), 2.06 (s, 3H), 1.78 (s, 3H),
1.73 (s, 3H) ppm; 13C{1H} NMR (90 MHz, CDCl3): δ 141.7, 140.0, 139.3, 137.7, 137.6, 136.1, 135.4,
135.2, 133.4, 133.1, 132.2, 129.6, 129.5, 128.8, 128.6, 128.0, 127.7, 127.2, 127.0, 126.7, 126.5, 126.1,
126.0, 21.2, 20.8, 19.0, 18.9 ppm. HRMS (MALDIꢀTOF) m/z calcd for C60H48 [M]+: 768.3756, found:
768.3774; IR (ATR) ν (cmꢀ1): 3038, 2918, 1601, 1441, 1373, 763, 702.
4,4’’’’’-Bis(2,4,6-trimethylbiphenyl-3-yl)-1,1’:4’,1’’:4’’,1’’’:4’’’,1’’’’:4’’’’,1’’’’’-sexinaphthalene
(6e). From the same experiment used to obtained 3e, an additional product was isolated that corresponded
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to the hexanaphthalene 6e. Light red powder, 38 mg, yield: 22%; mp 278ꢀ281 °C; H NMR (360 MHz,
CDCl3): δ 7.85 ꢀ 7.62 (m, 22H), 7.53 ꢀ 7.29 (m, 24H), 7.23 and 7.21 (two overlapping s, 1H + 1H), 2.17
(two overlapping s, 3H + 3H), 2.12 (s, 3H), 2.08 (s, 3H), 1.79 (s, 3H), 1.75 (s, 3H); 13C NMR (101 MHz,
CDCl3): δ 141.7, 140.0, 139.4, 138.7, 137.6, 136.1, 135.4, 135.2, 133.4, 133.2, 132.3, 129.7, 129.5, 128.8,
128.6, 127.8, 126.7, 126.6, 126.1, 21.2, 20.1, 19.0 ppm. HRMS (MALDIꢀTOF) m/z calcd for C90H66
[M]+:1146.5159, found: 1146.5198; IR (ATR) ν (cmꢀ1): 30378, 2918, 2856, 1371, 838, 760, 702.
4, 4''- Bis(2,3,5,6-tetramethylphenyl)-1,1':4',1''-ternaphthalene (3f). Following the general
procedure, ternaphthalene (114 mg, 0.300 mmol) was allowed to react with 1,2,4,5ꢀtetramethylbenzene
(161 mg, 1.200 mmol). Column chromatography: silica gel, hexane : AcOEt 400 : 1 (hexane : AcOEt 50 :
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1, Rf = 0.42). White powder, 60 mg, yield: 31%; mp 165ꢀ168 °C; H NMR (360 MHz, CDCl3): δ 7.74 ꢀ
7.63 (m, 8H), 7.49 ꢀ 7.37 (m, 10H), 7.15 (s, 2H), 2.37 (two overlapping s, 6H + 6H), 1.96 (s, 6H), 1.91 (s,
6H) ppm. 13C{1H} NMR (90 MHz, CDCl3): δ 140.2, 139.9, 138.62, 128.56, 137.5, 133.7, 133.3, 133.2,
133.14, 133.11, 132.4, 130.8, 127.9, 127.7, 127.1, 127.0, 126.5, 126.4, 126.33, 126.31, 125.98, 125.95,
20.4, 17.34 and 17.25 (partial overlap of the latter two signals) ppm. HRMS (MALDIꢀTOF) m/z calcd for
C50H44 [M]+: 644.3438, found 644.3441; IR (ATR) ν (cmꢀ1): 3039, 2918, 2863, 1466, 1369, 824, 761.
4,4’’’’’-Bis(2,3,5,6-tetramethylphenyl)-1,1':4',1'':4’’,1’’’:4’’’,1’’’’:4’’’’,1’’’’’- sexinaphthalene (6f).
From the same experiment used to obtained 3f, an additional product was isolated that corresponded to
the hexanaphthalene 6f. Peach powder, 52 mg, yield: 34%; mp 256ꢀ259 °C; 1H NMR (360 MHz, CDCl3):
δ 7.86 ꢀ 7.65 (m, 20H), 7.49 ꢀ 7.39 (m, 16H), 7.15 (s, 2H), 2.39 – 2.37 (two overlapping s, 6H + 6H), 1.97
(s, 6H), 1.93 (s, 6H); 13C{1H} NMR (62.5 MHz, CDCl3): δ 140.29, 140.28, 139.9, 138.8, 138.7, 138.52,
138.48, 137.5, 133.8, 133.3, 133.14, 133.11, 132.5, 130.9, 128.0, 127.8, 127.1, 126.5, 126.4, 126.1, 126.0,
20.4, 17.4, 17.3. HRMS (MALDIꢀTOF) m/z calcd for C80H62 [M]+: 1022.4852, found: 1022.4870; IR
(ATR) ν (cmꢀ1): 3038, 2917, 1370, 826, 759.
4, 4’’’-Dimesityl-1,1':4’,1’’:4’’,1’’’ – quaternaphthalene (4a). Following the general procedure,
quaternaphthalene (203 mg, 0.400 mmol) was allowed to react with mesitylene (192 mg, 222 ꢂL, 1.600
mmol). Column chromatography: silica gel, hexane : AcOEt 70 : 1 (Rf = 0.29). Offꢀwhite powder, 271
mg, yield: 91%; mp 203ꢀ205 °C; 1H NMR (360 MHz, CDCl3): δ 7.84ꢀ7.62 (m, 12H), 7.56 ꢀ 7.51 (m, 2H),
7.49 ꢀ 7.35 (m, 10H), 7.11 ꢀ 7.10 (two overlapping s, 2H + 2H), 2.46 (s, 6H), 2.08 (s, 6H), 2.04 (s, 6H);
13C{1H} NMR (101 MHz, CDCl3): δ 139.0, 138.8, 138.7, 138.6, 138.5, 137.72, 137.71, 137.2, 133.4,
133.3, 133.2, 132.3, 128.3, 127.8, 127.2, 127.1, 126.5, 126.1, 126.0, 21.3, 20.7. HRMS (MALDIꢀTOF)
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m/z calcd for C58H46 [M]+: 742.3594, found : 742.3605; IR (ATR) ν (cmꢀ1): 3040, 2952, 2917, 2861, 1571,
1375, 839, 762.
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4, 4’’’-Bis(2,3,4,5,6-pentamethylphenyl)-1,1’:4’,1’’:4’’,1’’’-quaternaphthalene (4b). Following the
general procedure, quaternaphthalene (152 mg, 0.300 mmol) was allowed to react with 1,2,3,4,5ꢀ
pentamethyl benzene (178 mg, 1.201 mmol). Column chromatography: silica gel, hexane : AcOEt 100 : 1,
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(hexane : AcOEt 70 : 1, Rf = 0.13). Offꢀwhite powder, 227 mg, yield: 95%; mp 212ꢀ215 °C; H NMR
(360 MHz, CDCl3): δ 7.83ꢀ7.37 (m, 24H), 2.44 (s, 6H), 2.38 (two overlapping s, 6H + 6H), 2.04 (s, 6H),
1.99 (s, 6H); 13C NMR (62.5 MHz, CDCl3): δ 141.0, 138.82, 138.76, 138.54, 138.49, 137.6, 137.4, 134.4,
133.3, 133.2, 132.73, 132.69, 132.6, 128.0, 127.8, 127.1, 126.71, 126.69, 126.1, 125.9, 18.6, 18.55, 18.46,
17.1, 16.9, 16.8 ppm. HRMS (MALDIꢀTOF) m/z calcd for C62H54 [M]+: 798.4220, found: 798.4198; IR
(ATR) ν (cmꢀ1): 3038, 2915, 1508, 1372, 839, 760.
4, 4’’’- Bis(2,4,6-triethylphenyl)-1,1’:4’,1’’:4’’,1’’’-quaternaphthalene (4c). Following the general
procedure, quaternaphthalene (152 mg, 0.300 mmol) was allowed to react with 1,3,5ꢀtriethylbenzene (195
mg, 226 ꢂL, 1.200 mmol). Column chromatography: silica gel, hexane:AcOEt 60:1 (Rf = 0.26). Paleꢀ
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yellow powder, 191 mg, yield: 77%; mp 165ꢀ168 °C; H NMR (360 MHz, CDCl3): δ 7.83 ꢀ 7.62 (m,
12H), 7.55 ꢀ 7.49 (m, 4H), 7.43 ꢀ 7.33 (m, 8H), 7.16 (s, 2H), 7.15 (s, 2H), 2.80 (q, J = 7.5 Hz, 4H), 2.43 ꢀ
2.28 (m, 8H), 1.42 (t, J = 7.5 Hz, 6H), 1.14 ꢀ 1.06 (m, 12H); 13C{1H} NMR (62.5 MHz, CDCl3): δ 143.8,
143.2, 143.1, 138.8, 138.7, 138.6, 138.5, 138.4, 137.7, 136.0, 133.23, 133.19, 133.15, 133.06, 127.79,
127.76, 127.66, 127.14, 127.07, 126.6, 126.1, 126.0, 125.9, 125.33, 125.30, 29.0, 27.03, 26.96, 15.9, 15.8,
15.7 ppm. HRMS (MALDIꢀTOF) m/z calcd for C64H58 [M]+: 826.4533, found 826.4538; IR (ATR) ν (cmꢀ
1): 3040, 2962, 2931, 2870, 1458, 1421, 1372, 838, 761.
4, 4’’’- Bis(4-tert-butyl-2,6-dimethylphenyl)-1,1’:4’,1’’:4’’,1’’’-quaternaphthalene (4d). Following
the general procedure, quaternaphthalene (152 mg, 0.300 mmol) was allowed to react with 5ꢀtertꢀbutylꢀmꢀ
xylene (195 mg, 225 ꢂL, 1.200 mmol). Column chromatography: silica gel, hexane:AcOEt 70 : 1 (Rf =
0.22). White powder, 130 mg, yield: 52%; mp 219ꢀ222 °C; 1H NMR (360 MHz, CDCl3): δ 7.81 ꢀ 7.62 (m,
12H), 7.52 ꢀ 7.48 (m, 4H), 7.40 ꢀ 7.37 (m, 8H), 7.27 (broad s, 4H), 2.11 (s, 6H), 2.07 (s, 6H), 1.45 (s,
18H); 13C{1H} NMR (90 MHz, CDCl3): δ 150.3, 139.2, 139.1, 138.80, 138.75, 138.6, 138.51, 138.49,
137.6, 136.9, 136.66, 136.65, 133.4, 133.3, 133.2, 132.3, 128.0, 127.8, 127.1, 126.4, 126.04, 125.96,
124.5, 34.6, 31.7, 21.1 ppm. HRMS (MALDIꢀTOF) m/z calcd for C64H58 [M]+: 826.4533, found:
826.4551; IR (ATR) ν (cmꢀ1): 3040, 2953, 2865, 1481, 1373, 964, 837, 761.
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Octinaphthalene 8d. From the same experiment used to obtained 4d, trace amount of an additional
product was isolated that corresponded to the octinaphthalene 8d. HRMS (MALDIꢀTOF) m/z calcd for
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104H82 [M]+: 1330.6411, found: 1330.6428.
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general procedure, quaternaphthalene (152 mg, 0.300 mmol) was allowed to react with 2ꢀ
phenylmesitylene (235 mg, 1.200 mmol). Column chromatography: silica gel, hexane:AcOEt 50:1 (Rf =
0.35). White powder, 160 mg, yield: 60%; mp 250ꢀ253 °C; 1H NMR (360 MHz, CDCl3): δ 7.80 ꢀ 7.61 (m,
14H), 7.53 ꢀ 7.28 (m, 20H), 7.22 (s, 1H), 7.21 (s, 1H), 2.16 (s, 6H), 2.12 (s, 3H), 2.07 (s, 3H), 1.79 (s, 3H),
1.75 (s, 3H); 13C{1H} NMR (90 MHz, CDCl3): δ 141.8, 140.0, 139.4, 138.8, 138.5, 137.7, 137.6, 136.1,
135.4, 135.2, 133.4, 133.2, 132.3, 129.7, 129.6, 128.9, 128.6, 128.1, 127.7, 127.1, 126.6, 126.1, 21.2, 20.8,
19.0, 18.9 ppm. HRMS (MALDIꢀTOF) m/z calcd for C70H54 [M]+: 894.4220, found: 894.4224; IR (ATR)
ν (cmꢀ1): 3038, 2949, 2918, 2860, 1441, 1372, 952, 838, 761.
4, 4’’’- Bis(2,3,5,6-tetramethylphenyl)-1,1':4’,1’’:4’’,1’’’ –quaternaphthalene (4f). Following the
general procedure, quaternaphthalene (152 mg, 0.300 mmol) was allowed to react with 1,2,4,5ꢀ
tetramethylbenzene (161 mg, 1.200 mmol). Column chromatography: silica gel, hexane : AcOEt 50 : 1,
Rf = 0.35. Pale yellow powder, 86 mg, yield: 37%; mp 212ꢀ215 °C; 1H NMR (360 MHz, CDCl3): δ 7.82 ꢀ
7.64 (m, 12H), 7.51 ꢀ 7.35 (m, 12H), 7.15 (s, 2H), 2.38 (s, 6H), 2.37 (s, 6H), 1.96 (s, 6H), 1.92 (s, 6H).
13C{1H} NMR (90 MHz, CDCl3): δ 140.3, 140.0, 138.80, 138.76, 138.74, 138.56, 138.55, 137.55, 137.54,
133.8, 133.31, 133.27, 133.23, 133.20, 133.14, 133.11, 132.5, 130.9, 128.0, 127.78, 127.76, 127.1, 126.49,
126.46, 126.38, 126.35, 126.07, 126.02, 126.00, 125.98, 20.41, 20.39, 17.34, 17.32, 17.25 ppm. HRMS
(MALDIꢀTOF) m/z calcd for C60H50 [M]+: 770.3907, found: 770.3874; IR (ATR) ν (cmꢀ1): 3038, 2918,
2864, 1450, 1378, 826, 764..
Octinaphthalene 8f. From the same experiment used to obtained 4f, an additional product was isolated
that corresponded to the octinaphthalene 8f. Purple powder, 8 mg, yield: 4%; 1H NMR (360 MHz,
CDCl3): δ 7.87 ꢀ 7.66 (m, 28H), 7.48 ꢀ 7.42 (m, 20H), 7.15 ( s, 2H), 2.37 (s, 12H), 1.97 (s, 6H), 1.93 (s,
6H). HRMS (MALDIꢀTOF) m/z calcd for C90H66 [M]+: 1274.5785, found: 1274.5852.
ACKNOWLEDGEMENTS
Financial support from Ministerio de Ciencia e Innovación (MICINN) of Spain (Projects
CTQ2008ꢀ05409ꢀC02ꢀ01, CTQ2009ꢀ07881, CTQ2011ꢀ22649 and Consolider Ingenio 2010
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(CSD2007ꢀ00006)). A Ramón y Cajal scholarship to A. S. (MEC, Spain, RYCꢀ2006ꢀ001425),
DURSIꢀGeneralitat de Catalunya (SGR2009ꢀ1441) and China Scholarship Council (CSC
scholarship) are gratefully acknowledged. We thank Dr. J. Orduna for the MALDIꢀTOF spectra.
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Copies of the NMR and MS spectra, and the details of experiment optimization are available free of
charge via the Internet at http://pubs.acs.org.
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