Synthesis, Resolution, and Applications of 1,16-Dihydroxytetraphenylene as a Novel Building Block in Molecular Recognition and Assembly

Article abstract of DOI:10.1021/jo0302408

This paper concerns the synthesis of 1,16-dihydroxytetraphenylene (DHTP) (2) by employing a novel NBS bromination route. (±)-DHTP 2 was successfully resolved into its optical antipodes and converted to (±)-1,16-bis(diphenylphosphino)tetraphenylene (BPTP) (26), whose platinum complex BPTP-PtCl₂ (27) was also obtained. As a hydrogen bond donor, racemic and optically active DHTP 2 was allowed to assemble with 4,4′-bipyridine to form single crystals of good quality. X-ray Diffraction studies of these crystals revealed that the crystallographic packing of the hydrogen bonded complex between (±)-2 and 4,4′-bipyridine was different from the one formed from (S)-2 and 4,4′-bipyridine. It was found that an infinite zigzag chain with alternate chirality was formed in the assembly of (±)-2 and 4,4′-bipyridine, while (S)-2 and 4,4′-bipyridine failed to show the same assembly pattern. The reason (±)-2 formed an alternate and zigzag chain with 4,4′-bipyridine was most likely due to the inherent stability of this supramolecular assembly. The chiral recognition between 2 and optically active BINAP under the direction of platinum(II) has also been examined. ¹H and ³¹P NMR spectroscopic studies demonstrated that there was an obvious discrimination of 2 between the enantiomers of BINAP-PtCO₃.

Full text of DOI:10.1021/jo0302408

Syn th esis, Resolu tion , a n d Ap p lica tion s of
1,16-Dih yd r oxytetr a p h en ylen e a s a Novel Bu ild in g Block in
Molecu la r Recogn ition a n d Assem bly1
J ian-Feng Wen,2 Wei Hong,2 Ke Yuan,3 Thomas C. W. Mak,4 and Henry N. C. Wong*,2,4,5
Shanghai-Hong Kong J oint Laboratory in Chemical Synthesis, Shanghai Institute of Organic Chemistry,
The Chinese Academy of Sciences, 354 Feng Lin Road, Shanghai 200032, China, State Key Laboratory of
Organometallic Chemistry, Shanghai Institute of Organic Chemistry, The Chinese Academy of Sciences,
354 Feng Lin Road, Shanghai 200032, China, Department of Chemistry, The Chinese University of Hong
Kong, Shatin, New Territories, Hong Kong, and Central Laboratory, Institute of Molecular Technology for
Drug Discovery and Synthesis, The Chinese University of Hong Kong, Shatin,
New Territories, Hong Kong
hncwong@cuhk.edu.hk
Received J uly 28, 2003
This paper concerns the synthesis of 1,16-dihydroxytetraphenylene (DHTP) (2) by employing a
novel NBS bromination route. (()-DHTP 2 was successfully resolved into its optical antipodes and
converted to (()-1,16-bis(diphenylphosphino)tetraphenylene (BPTP) (26), whose platinum complex
BPTP-PtCl2 (27) was also obtained. As a hydrogen bond donor, racemic and optically active DHTP
2 was allowed to assemble with 4,4′-bipyridine to form single crystals of good quality. X-ray
Diffraction studies of these crystals revealed that the crystallographic packing of the hydrogen
bonded complex between (()-2 and 4,4′-bipyridine was different from the one formed from (S)-2
and 4,4′-bipyridine. It was found that an infinite zigzag chain with alternate chirality was formed
in the assembly of (()-2 and 4,4′-bipyridine, while (S)-2 and 4,4′-bipyridine failed to show the same
assembly pattern. The reason (()-2 formed an alternate and zigzag chain with 4,4′-bipyridine was
most likely due to the inherent stability of this supramolecular assembly. The chiral recognition
between 2 and optically active BINAP under the direction of platinum(II) has also been examined.
1H and 31P NMR spectroscopic studies demonstrated that there was an obvious discrimination of
2 between the enantiomers of BINAP-PtCO3.
SCHEME 1
In tr od u ction
Tetraphenylene (1) is a structurally highly intriguing
molecule that possesses a ground state D2d geometry
(Scheme 1). Several research teams have been actively
engaged in the syntheses6 and various physical6,7 studies
of 1 and its analogues.8
(1) Taken in part from the doctoral thesis of J .F.W., Shanghai
Institute of Organic Chemistry, The Chinese Academy of Sciences,
Shanghai, China, 2003.
(2) Shanghai-Hong Kong J oint Laboratory in Chemical Synthesis,
In view of the interesting properties of tetraphenylene
(1), we have commenced a program with the aim to
prepare five tetraphenylenols 2-69 as shown in Scheme
2. Due to the very high barrier to ring inversion of 1,7 it
is worthy to note that 2, 3, and 5 could in principle be
The Chinese Academy of Sciences.
(3) State Key Laboratory of Organometallic Chemistry, The Chinese
Academy of Sciences.
(4) Department of Chemistry, The Chinese University of Hong Kong.
(5) Institute of Molecular Technology for Drug Discovery and
Synthesis, The Chinese University of Hong Kong.
(6) For reviews, see: (a) Mak, T. C. W.; Wong, H. N. C. In
Comprehensive Supramolecular Chemistry; MacNicol, D. D., Toda, F.,
Bishop, P., Eds.; Pergamon Press: Oxford, 1996; Vol. 6, pp 351-369.
(b) Mak, T. C. W.; Wong, H. N. C. Top. Curr. Chem. 1987, 140, 141-
164. (c) Rajca, A.; Safronov, A.; Rajca, S.; Shoemaker, R. Angew. Chem.,
Int. Ed. Engl. 1997, 36, 488-491. (d) Rajca, A.; Safronov, A.; Rajca,
S.; Wongsriratanakul, J . J . Am. Chem. Soc. 2000, 122, 3351-3357.
(e) Rajca, A.; Wang, H.; Bolshov, P.; Rajca, S. Tetrahedron 2001, 57,
3725-3735. (f) Rathore, R.; Magueres, P. L.; Lindeman, S. V.; Kochi,
J . Angew. Chem., Int. Ed. 2000, 39, 809-812. (g) Iyoda, M.; Kabir, S.
H. M.; Vorasingha, A.; Kuwatani, Y.; Yoshida, M. Tetrahedron Lett.
1998, 39, 5393-5396. (h) Kabir, S. M. H.; Iyoda, M. Synthesis 2000,
1839-1842. (i) Kabir, S. M. H.; Hasegawa, M.; Kuwatani, Y.; Yoshida,
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159-165.
(7) (a) Figeys, H. P.; Dralants, A. Tetrahedron Lett. 1971, 3901-
3904. (b) Finder, C. J .; Chung, D.; Allinger, N. L. Tetrahedron Lett.
1972, 4677-4680. (c) Gust, D.; Senkler, G. H., J r.; Mislow, K. J . Chem.
Soc., Chem. Commun. 1972, 1345-1345. (d) Senkler, G. H., J r.; Gust,
D.; Riccobono, P. X.; Mislow, K. J . Am. Chem. Soc. 1972, 94, 8626-
8627. (e) Rashi-Ranjbar, P.; Man, Y.-M.; Sandstro¨m, J .; Wong, H. N.
C. J . Org. Chem. 1989, 54, 4888-4892.
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123, 1755-1759. (c) Marsella, M. J . Acc. Chem. Res. 2002, 35, 944-
951 and references therein.
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C. Org. Lett. 2003, 5, 823-826.
10.1021/jo0302408 CCC: $25.00 © 2003 American Chemical Society
Published on Web 10/14/2003
8918
J . Org. Chem. 2003, 68, 8918-8931

1,16-Dihydroxytetraphenylene in Molecular Recognition and Assembly
SCHEME 2
We report herein our efforts in the synthesis and
resolution of 2. We also present the crystallographic
packing features of 2 in its racemic and chiral forms with
4,4′-bipyridine, as well as the NMR study on the likely
chiral recognition in the interaction between enantiomers
of 2 and those of BINAP under the direction of platinum-
(II). Furthermore, as part of a continuing interest in the
design of substituted tetraphenylenes, we would like to
report the conversion of 2 through its corresponding
triflate to a diphenylphosphine derivative and the use of
this bis(diphenylphosphine) derivative in platinum(II)
complexation.
Resu lts a n d Discu ssion
Syn th esis a n d Resolu tion of 1,16-Dih yd r oxytet-
r a p h en ylen e (DHTP ) (2). Since the first successful
synthesis of 1 was reported in 1943,13 much effort has
been devoted to the synthesis of 1 and its derivatives.6
Following the earlier works of Mislow14a and our group,14b
an eight-membered ring compound 9 could be constructed
by bis-alkylation of the dibromide 715 with the tetraester
816 as can be seen in the retrosynthetic pathway shown
in Scheme 3, which also illustrates that additional steps
would convert 9 to the target molecule 2 via 1,16-
dimethoxytetraphenylene (13). It is noteworthy that two
hydroxyl groups must be introduced to carbon-1 and
carbon-16 in a regiospecific manner. We have therefore
chosen to begin the synthesis employing a known dibro-
mide, namely, 2,2′-bis(bromomethyl)-6,6′-dimethoxybi-
phenyl (7),15 as the precursor.
Compound 9 was only generated in a disappointing
yield of 20% when toluene was used as the solvent.
However, optimization procedures revealed that dioxane
was much more superior as a solvent, and as a result,
the yield was upgraded to 40%. After repeated trials of
this cyclization step, it was eventually found that the
molar ratio of starting materials was crucial to the
reaction outcome. Thus, when we adjusted the molar
ratio of 8:potassium:7 to 1:0.8:0.7, the yield of 9 was
increased to 68% (Scheme 4). In the subsequent step, 9
was allowed to undergo concomitant saponification and
decarboxylation14b with KOH in refluxing ethylene glycol
to provide diacid 14 in 91% yield. Lead tetraacetate
oxidation converted 14 into 10 in a meager 33% yield.
Bromination of 10 expectedly furnished dibromide 15,
resolved into their optical antipodes. On the other hand,
4 and 6 are intrinsically achiral. Because of their non-
planar and defined three-dimensional structures, 2-6 are
able to serve as chiral and nonchiral building blocks with
their oxygen atoms being reactive sites. Geometrically,
3 is a linear unit containing reactive sites whose angle
is 180°, while the reactive sites of 4 comprise an angle of
90° (Scheme 2). In this manner, the hydroxyl groups of
these building blocks could be interconnected with guest
molecules via noncovalent interaction10 or with central
metal linkages via covalent interaction,11,12 forming
ordered linear and two- and three-dimensional scaffolds.
(13) Rapson, W. S.; Shuttleworth, R. G.; van Niejerk, J . J . Chem.
Soc. 1943, 326-327.
(10) Inter alia, see: (a) Comprehensive Supramolecular Chemistry;
Sauvage, J .-P., Hosseini, M. W., Eds.; Pergamon Press: Oxford, 1996;
Vol. 9. (b) Fyfe, M. C. T.; Stoddart, J . F. Acc. Chem. Res. 1997, 30,
393-401. (c) Stang, P. J .; Olenyuk, B. Acc. Chem. Res. 1997, 30, 502-
518. (d) Fujita, M. Chem. Soc. Rev. 1998, 27, 417-426.
(14) (a) Dvorken, L. V.; Smyth, R. B.; Mislow, K. J . Am. Chem. Soc.
1958, 80, 486-492. (b) Wong, H. N. C.; Sondheimer, F. J . Org. Chem.
1980, 45, 2438-2440.
(15) (a) Zhang, A.-M. Ph.D. Thesis, Shanghai Institute of Organic
Chemistry, The Chinese Academy of Sciences, Shanghai, China, 2001.
(b) Kanoh, S.; Muramoto, H.; Kobayashi, N.; Motoi, M.; Suda, H. Bull.
Chem. Soc. J pn. 1987, 60, 3659-3662. (c) Gajewski, J . J .; J imenez, J .
L. J . Am. Chem. Soc. 1986, 108, 468-474. (d) Newman, M.; Lilje, K.
C. J . Org. Chem. 1979, 44, 4944-4946. (e) Corey, E. J .; Suggs, J . W.
Tetrahedron Lett. 1975, 2647-2650. (f) Tichy, M.; Budesinsky, M.;
Gunterova, J .; Zavada, J .; Podiaha, J .; Cisarova, I. Tetrahedron 1999,
35, 7893-7906. (g) Godfrey, I. M.; Sargent, M. V.; Elix, J . A. J . Chem.
Soc., Perkin. Trans. 1 1974, 1353-1354. (h) Adams, R.; Baker, B. R.
J . Am. Chem. Soc. 1941, 63, 535-537. (i) J ohnstone, R. A. W.; Rose,
M. E. Tetrahedron 1979, 35, 2169-2173. (j) Goleman, R. S.; Guernon,
J . M.; Roland, J . T. Org. Lett. 2000, 2, 277-280. (k) D´ıaz, E.; Guzma`n,
A.; Cruz, M.; Mares, J .; Ram´ıez, D. J .; J oseph-Nathan, P. Org. Magn.
Reson. 1980, 13, 180-186. (l) Gruter, G. J . M.; Akkerman, O. S.;
Bickelhanpt, F. J . Org. Chem. 1994, 59, 4473-4481.
(11) Rowan, S. J .; Cantrill, S. J .; Cousins, G. R. L.; Sanders, J . K.
M.; Stoddart, J . F. Angew. Chem., Int. Ed. 2002, 41, 898-952.
(12) Quadrivalent metal BINOLates (BINOL is 1,1′-binaphthol) are
well-known and have been shown to exhibit chiral recognition and
asymmetric catalytic properties. For leading references, see: (a)
Mikami, K.; Shimizu, M. Chem. Rev. 1992, 92, 1021-1050. (b) Terada,
M.; Matsumoto, Y.; Nakamura, Y.; Mikami, K. Inorg. Chim. Acta 1999,
296, 267-272. (c) Mikami, K.; Matsukawa, S.; Volk, T.; Terada, M.
Angew. Chem., Int. Ed.. 1997, 36, 2768-2771. (d) Corey, E. J .; Lee, T.
W. Chem. Commun. 2001, 1321-1329. (e) Corey, E. J .; Letavic, M. A.;
Noe, M. C.; Sarshar, S. Tetrahedron Lett. 1994, 35, 7553-7556. (f)
Shibasaki, M.; Kanai, M.; Funabashi, K. Chem. Commun. 2002, 1989-
1999. (g) Tanski, J . M.; Wolczanski, P. T. Inorg. Chem. 2001, 40, 2026-
2033. (h) Kuntz, B. A.; Ramachandran, R.; Taylor, N. J .; Guan, J .;
Collins, S. J . Organomet. Chem. 1995, 497, 133-142. (i) Boyle, T. J .;
Barnes, D. L.; Heppert, J . A.; Morales, L.; Takusagawa, F.; Connolly,
J . Organometallics 1992, 11, 1112-1126.
(16) (a) Bischoff, C. A.; Rach, C. Ber. 1884, 17, 2781-2788. (b)
Conrad, M.; Bischoff, C. A. Liebig Ann. Chem. 1882, 214, 68-72.
J . Org. Chem, Vol. 68, No. 23, 2003 8919

Wen et al.
SCHEME 3
SCHEME 4
which upon dehydrobromination with DBN14b gave 1,12-
dimethoxydibenzo[a,c]cyclooctene (16) in an extremely
low yield (below 23%). Moreover, despite many attempts,
we failed to obtain a sample of 16 with sufficient purity
for 1H NMR spectroscopic studies. Fortunately, the
structure of 16 was substantiated unequivocally by an
X-ray diffraction analysis (Figure 1). To complete the
synthesis of 2, a tetrabromide 17 was designed, which
should be obtainable from 16. However, to our surprise,
all attempts to brominate 16 were unfruitful, and only
intractable materials resulted. One explanation for this
discrepancy is the likely competing electrophilic aromatic
substitution of the benzene rings, leading to undesired
aryl bromides.
In view of the low-yield reaction in the preparation of
16, as well as the difficulty encountered in its bromina-
tion, we turned our attention to the radical-initiated
bromination of 10, in the hope of generating an appropri-
ate bromide for further manipulation. This avenue was
first explored by treatment of 10 with 2 molar equiv of
NBS in the presence of dibenzoyl peroxide. It was found
that this reaction afforded a mixture that was not easily
identified by NMR spectroscopic studies. The mass
spectrum of this mixture, on the other hand, did indicate
the formation of a tribromide. It was fortunate that a
chloroform solution of this mixture led to the formation
of crystals suitable for an X-ray crystallographic analysis.
F IGURE 1. ORTEP drawing of 16.
Thus, the X-ray diffraction result17 depicted the structure
of tribromide 18, presumably formed through a radical
mechanism whose full details are not yet known to us.
The yield of 18 from 10 was further improved to 78%
when 3 molar equiv of NBS were used (Scheme 5). It was
also illustrated in Scheme 5 that dehydrobromination of
(17) Supporting Information.
8920 J . Org. Chem., Vol. 68, No. 23, 2003

1,16-Dihydroxytetraphenylene in Molecular Recognition and Assembly
SCHEME 5
18 with DBN led to the formation of dibromide 11, which
was the desired precursor for the preparation of 12.
Indeed, when 11 was allowed to undergo dehydrobromi-
nation with KO-t-Bu in the presence of furan,14b an
unexpectedly high yield (61%) of the bis-endoxide 12 was
afforded. From the dehydrobromination of 11 presumably
a strained cyclic alkyne was generated, which underwent
a Diels-Alder reaction with furan to form 12. Deoxy-
genation of 12 with low-valent titanium18 produced in
situ by reduction of titanium(IV) chloride with lithium
aluminum hydride in the presence of triethylamine
furnished 1,16-dimethoxytetraphenylene (13) in 80%
yield, whose structure was confirmed also by an X-ray
diffraction study.17 Eventually, the desired 2 was ob-
tained in 97% yield by treatment of 13 with boron
tribromide (Scheme 5).19
F IGURE 2. Resolution of (()-2 through chiral HPLC (AD
column): retention times of (S)-2 and (R)-2 were 11.6 and 17.5
min, respectively.
The observation of the antipodes of 2 was first realized
through HPLC on a chiral column (Figure 2). It was also
found that the diastereomeric bis-(S)-camphorsulfonates
of (()-2, namely, 19 and 20 were chromatographically
separable using a 6:1 mixture of benzene and ethyl actate
as an eluent. Due to the fact that the absolute configu-
ration of the (S)-camphorsulfonyl group was defined, an
X-ray crystallographic analysis of the less polar bis-
camphorsulfonate 19 therefore led us to confirm the
absolute structure of its appended 2 to be of (S)-config-
uration.17 In this manner, the absolute stereochemistry
of 20 with an appended (R)-2 was also indirectly con-
firmed. Subsequent desulfonylation generated the enan-
tiomerically pure (S)-2 and (R)-2, whose optical purities
were found to be >99% by HPLC on a chiral column.20
The circular dichroism (CD) spectra of (S)-2 and (R)-2
were also recorded in methanol (Figure 3). As can be
seen, the CD spectrum of (S)-2 showed strong bands at
196.6(-), 208.8(-), and 214.8(+) nm with a succession
of weaker absorption bands at around 231.6(-) and
247.0(+) nm. On the other hand, the CD spectrum of
(R)-2 showed an almost opposite curve, i.e., strong bands
at 196.6(+), 199.0(+), and 215.2(-) nm with weaker
bands at 231.4(+) and 249.0(-) nm.
F IGURE 3. CD spectra of (S)-2 and (R)-2 in methanol.
as metal coordination sites21 prompted us to undertake
the reaction sequence as shown in Scheme 7 in order to
realize 1,16-bis(diphenylphosphino)tetraphenylene (27).
The pivotal step in Scheme 7 is the palladium-catalyzed
reaction, which is capable of converting triflates to other
functionalities. Thus, 2 was readily converted into the
bis-triflate 21 with triflic anhydride in the presence of
pyridine.22 Monophosphinylation of 21 with diphenylphos-
pine oxide proceeded smoothly under Hayashi’s condi-
tions23 to afford 22 in 97% yield. Reduction of 22 with
trichlorosilane-triethylamine24 gave the corresponding
Syn th esis of 1,16-Bis(diph en ylph osph in o)tetr aph e-
n ylen e (BP TP ) (26). The quest for substituted tet-
raphenylenes that contain appropriate functional groups
(21) Kumobayashi, H.; Miura, T.; Sayo, N.; Saito, T.; Zhang, X.
Synlett. 2001, 1055-1064.
(18) Xing, Y. D.; Huang, N. Z. J . Org. Chem. 1982, 47, 140-142.
(19) McOmie, J . F.; Watts, M. L.; West, D. E. Tetrahedron 1968,
24, 2289-2292.
(20) (a) Ng, M.-K.; Chow, H.-F.; Chan, T.-L.; Mak, T. C. W.
Tetrahedron Lett. 1996, 37, 2979-2982. (b) Chow, H.-F.; Wan, C.-W.;
Ng, M.-K. J . Org. Chem. 1996, 61, 8712-8714.
(22) Cai, D.; Payack, J . F.; Bender, D. R.; Hughes, D. L.; Verhoeven,
T. R.; Reider, P. J . Org. Synth. 1996, 76, 8-11.
(23) Uozumi, Y.; Tanahashi, A.; Lee, S.-Y.; Hayashi, T. J . Org. Chem.
1993, 58, 1945-1948.
(24) Takaya, H.; Akutagawa, S.; Noyori, R. Org. Synth. Coll. Vol.
1993, 8, 57-63.
J . Org. Chem, Vol. 68, No. 23, 2003 8921

Wen et al.
SCHEME 6
SCHEME 7
phosphine 23 in 89% yield. A subsequent nickel-catalyzed
coupling reaction21 of 23 with diphenylphosphine oxide
led to the desired bis-phosphinyltetraphenylene 25 in a
meager 18% yield, together with a reduction product 24
in 56% yield. This result indicates that under this
reaction condition, the first oxidative addition of nickel
onto 23 would proceed effectively but the resulting
organonickel triflate undergoes easily competing reduc-
tion steps to form 24. Reduction of 25 with, again,
trichlorosilane-triethylamine24 eventually furnished BPTP
26 in 60% yield. As shown in Scheme 7, the conversion
of 26 to a platinum complex was straightforward, giving
BPTP-PtCl2 27,25 whose structure was substantiated by
an X-ray diffraction analysis.17 It can be seen that a
seven-membered ring containing the diphosphine-che-
lated platinum that was linked to the tetraphenylene
skeleton was formed.
Cr ysta llogr a p h ic P a ck in g F ea tu r es of Assem bly
betw een 4,4′-Bip yr id in e a n d (()-2 a s w ell a s (S)-2.
The propensity of 1 and its derivatives to function as
hosts for a wide range of guest molecules via van der
Waals interaction has been extensively investigated.6a,b
The structural characteristics of the resulting clathrate
inclusion complexes based on these tetraphenylene skel-
etons have also been discussed in details.6a,b Hydrogen
bond interactions have also been utilized to construct a
variety of supramolecular assemblies.26 In light of the
(25) Tudor, M. D.; Becker, J . J .; White, P. S.; Gange´, M. R.
Organometallics 2000, 19, 4376-4380.
8922 J . Org. Chem., Vol. 68, No. 23, 2003

1,16-Dihydroxytetraphenylene in Molecular Recognition and Assembly
F IGURE 4. (a) Perspective view of the molecular aggregate of (()-2 and 4,4′-bipyridine. The thermal ellipsoids are drawn at the
35% probability level. (b) Perspective view of crystal packing (top view down the c-axis).
latter aspect, we considered it interesting to assess the
likely assembly via hydrogen bond interactions between
the hydrogen bond donor 2, whose two phenolic hydroxyl
groups are disposed with a specific geometry, and other
hydrogen bond acceptors. In this context, we first at-
tempted the molecular assembly between (()-2 and a
linear hydrogen bond acceptor, namely, 4,4′-bipyridine.
Thus, slow vaporization of a chloroform solution of (()-2
(1 molar equiv) and 4,4′-bipyridine (2 molar equiv) led
to the formation of single crystals of sufficiently good
quality for an X-ray crystallographic study (Figure 4).
Despite the experimental molar ratio of 1:2, 1H NMR
spectroscopic analysis of a CDCl3 solution of the single
crystals nonetheless depicted that the molecular complex
was composed of the hydrogen bond donor and acceptor
at a molar ratio of 1:1. As can be seen from Figure 4, the
molecular components in the molecular complex are
linked via hydrogen bonds between the protons of the
phenolic hydroxyl groups and the nitrogens of 4,4′-
bipyridine. In the crystal packing, an infinite zigzag chain
is formed, and many chains spread orderly in the ab
plane. Furthermore, in each zigzag chain, (S)-2 and (R)-2
are connected alternately with 4,4′-bipyridine via hydro-
gen bond interaction, thereby resulting in a continuous
heterochiral zigzag chain (Figure 5). Although in prin-
ciple two types of zigzag arrangements consisting purely
of either (S)-2 or (R)-2 could be formed, these infinite
homochiral chains have not been observed in the crystal
packing.
In a similar approach, single crystals were also readily
grown form the dichloromethane solution of (S)-2 (1
molar equiv) and 4,4′-bipyridine (2 molar equiv). Con-
trary to the aforementioned result, 1H NMR spectroscopic
analysis demonstrated that the composition of the mo-
lecular complex formed between (S)-2 and 4,4′-bipyridine
corresponded to a stoichiometric ratio of 1:2. The ORTEP
drawing of this molecular complex is shown in Figure 6.
As can be seen, the crystal packing pattern is consistent
with the composition, in which two 4,4′-bipyridine are
linked to one (S)-2. These discrete units, in turn, are not
linked together by hydrogen bonding (Figure 6).
Ch ir a l Recogn ition betw een 2 a n d BINAP . Gagne´
has examined the isomerization of a biphepPtX2 complex
(biphep is 2,2′-bis(diphenylphosphino)biphenyl and X2 is
1,1′-binaphthol) to gain insight into the mechanism of
diastereomeric interconversion.25 We would like to report
herein the results of our investigation of chiral recogni-
tion12,27 between 2 and 2,2′-bis(diphenylphosphino)-1,1′-
binaphthyl (BINAP) employing platinum(II) as a linker.
In this connection, two chiral BINAP platinum com-
plexes, namely, (S)-BINAP-PtCO3 (S)-28 and (R)-BI-
NAP-PtCO3 (R)-28 were prepared according to Gagne´’s
method.25 Thus, reaction of (S)-BINAP or (R)-BINAP with
(COD)PtCl2 provided the corresponding BINAP-PtCl2,
(26) (a) Fredericks, J . R.; Hamilton, A. D. In Comprehensive Su-
pramolecular Chemistry; Sauvage, J .-P., Hosseini, M. W., Eds.; Per-
gamon Press: Oxford, 1996; Vol. 9, pp 565-594. (b) Toda, F. In
Comprehensive Supramolecular Chemistry; MacNicol, D. D., Toda, F.,
Bishop, R., Eds.; Pergamon Press: Oxford, 1996; Vol. 6, pp 466-516.
(c) Vaidhyanathan, R.; Natarajan, S.; Rao, C. N. R. J . Mol. Struct. 2002,
608, 123-133. (d) Zhang, J .-H.; Liao, J .; Cui, X.; Yu, K.-B.; Zhu, J .;
Deng, J .-G.; Zhu, S.-F.; Wang, L.-X.; Zhou, Q.-L.; Chung, L.-W.; Ye, T.
Tetrahedron: Asymmetry 2002, 13, 1363-1366. (e) Toda, F.; Senzaki,
M.; Kuroda, R. J . Chem. Soc., Chem. Commun. 2002, 1788-1789. (f)
Hamilton, T. D.; Papaefstathiou, G. S.; MacGillivray, L. R. J . Am.
Chem. Soc. 2002, 124, 11606-11607. (g) Holy´, P.; Sehnal, P.; Tichy´,
M.; Za´vada, J .; C´ısarˇova´, I. Tetrahedron: Asymmetry 2003, 14, 245-
253.
(27) Some references for chiral recognition of optically active phenols
(such as BINOL) via covalent interaction under direction of metal
central linkages (such as Ti): (a) Boyle, T. J .; Eilerts, N. W.; Heppert,
J . A.; Takusagawa, F. Organometallics 1994, 13, 2218-2229 and
references therein. (b) Terada, M.; Matsumoto, Y.; Nakamura, Y.;
Mikami, K. Inorg. Chim. Acta 1999, 296, 267-272. (c) Mikami, K.;
Matsukawa, S.; Volk, T.; Terada, M. Angew. Chem., Int. Ed. 1997, 36,
2768-2771. (d) Huttenloch, M. E.; Dorer, B.; Rief, U.; Prosenc, M.-H.;
Schmidt, K.; Brintzinger, H. H. J . Organomet. Chem. 1997, 541, 219-
232. (e) Balsells, J .; Carroll, P. J .; Walsh, P. J . Inorg. Chem. 2001, 40,
5568-5574. (f) Hanawa, H.; Hashimoto, T.; Maruoka, K. J . Am. Chem.
Soc. 2003, 125, 1708-1709.
J . Org. Chem, Vol. 68, No. 23, 2003 8923

Wen et al.
F IGURE 5. (a) Hydrogen bonding between the two molecular components in the crystal structure of (()-2‚(C5H4N)2. The diol
and 4,4′-bipyridine molecules are alternately linked by O-H‚‚‚N hydrogen bonds to form a zigzag chain running parallel to the
c-axis. The chains are arranged to form a pleated sheet whose mean plane is normal to the b-axis. For simplicity, the tetrol
molecule is represented by its HO-C-C-C-C-OH fragment and the 4,4′-bipyridine molecule by a rigid rod. (b) View of the
crystal structure of (()-2‚(C5H4N)2 along the b-axis. For simplicity, the tetrol molecule is represented by its HO-C-C-C-C-OH
fragment and the 4,4′-bipyridine molecule by a rigid rod.
PtCO3 28, we observed the reactions of (S)-28 and (R)-
28 with (S)-2, (R)-2, and (()-2 by monitoring with 1H
NMR and 31P NMR spectroscopic methods. The matches
and molar quantities of these reactants are discussed
below, and the reaction of 28 and 2, forming 29, is shown
in Scheme 8. Experimentally, 28 and 2 were mixed in a
NMR tube with CDCl3 being the solvent. The mixture
was irradiated with supersonic waves to afford a clear
1
greenish solution, which was then studied by H NMR
and 31P NMR spectroscopy.
The reaction between (S)-2 and (S)-28 was first chosen
1
as an initial study (Figure 7). Figure 7a contains the H
NMR spectrum of 2, where a pair of doublets Y and Z
are characteristic. Figure 7b illustrates the 1H NMR and
31P NMR spectra of (S)-28, where peaks A and PA are
distinctive. When the molar ratio of (S)-28 and (S)-2 is
1:0.9, Figure 7c shows that in addition to the appearance
of the original 1H NMR absorption A and 31P NMR
absorption PA in Figure 7b, new absorptions B, C, D, and
PB are observed, which eventually become the major
peaks when the molar ratio of (S)-28 and (S)-2 is 1:1.6
as depicted in Figure 7d. It is worth mentioning that (S)-
28 and (S)-2 reacted with each other completely at a
molar ratio of 1:1 when the reaction was carried out in
refluxing CHCl3 (Figure 7e). However, it should be
F IGURE 6. (a) ORTEP drawing of the molecular complex of
(S)-2 and 4,4′-bipyridine. (b) Perspective view of crystal
packing.
pointed out that in our 1H NMR spectroscopic studies,
the peaks are too complicated, making a detailed proton
assignment difficult.
The next experiment concerned the mixing of (S)-28
with (R)-2 in an initial molar ratio of 1:1 (Figure 8). In
this manner, it was observed that the reaction between
these two chiral compounds was relatively slow and that
which were converted readily to the desired (S)-28 and
(R)-28, respectively, by reaction with Ag2CO3 in wet
dichloromethane under darkness. To examine the chiral
factor involved in the interaction between 2 and BINAP-
8924 J . Org. Chem., Vol. 68, No. 23, 2003

1,16-Dihydroxytetraphenylene in Molecular Recognition and Assembly
F IGURE 7. 1H NMR spectra of the reaction mixtures of (S)-28 and (S)-2, and at the top right corners of the spectra are the
1
1
corresponding 31P NMR spectra. (a) H NMR spectrum of 2. (b) H NMR spectrum of (S)-28. (c) S-2 and (S)-28 mixed at a molar
ratio of 1:0.9. (d) (S)-2 and (S)-28 mixed at a molar ratio of 1:1.6. (e) (S)-2 and (S)-28 mixed at an equal molar ratio and reacted
in refluxing CHCl3.
SCHEME 8
the time required for the mixture to become a greenish
solution under supersonication was much longer. In
comparison with the original 1H NMR and 31P NMR
spectra of the starting materials (Figures 7a and 7b),
J . Org. Chem, Vol. 68, No. 23, 2003 8925

Wen et al.
F IGURE 8. 1H NMR spectra of the reaction mixtures of (S)-28 and (R)-2, and at the top right corners of the spectra are the
corresponding 31P NMR spectra. (a) (S)-28 and (R)-2 mixed at a molar ratio of 1:1. (b) (S)-28 and (R)-2 mixed at a molar ratio of
1:1.8.
F IGURE 11. 1H NMR spectrum of the reaction mixtures of
F IGURE 9. 1H NMR spectrum of the reaction mixture of (S)-
(R)-28 and (S)-2 at a molar ratio of 1:1.3, and at the top right
28 and (()-2 at a molar ration of 1:3.3, and at the top right
corner of the spectrum is the corresponding 31P NMR spectrum.
corner of the spectrum is the corresponding 31P NMR spectrum.
When 1 molar equiv of (S)-28 was allowed to mix with
3.3 molar equiv of (()-2, the resulting 1H NMR spectrum
reveals a new set of proton NMR absorptions B, E, C, D,
F, and G, as well as 31P NMR absorptions PB and PE
(Figure 9). The spectra are essentially a combined
spectrum of Figures 7d and 8b, in which two diastereo-
mers are formed and the one formed from (S)-2 and (S)-
28 is the major component since B, C, D, and PB are more
distinct than E, F, G, and PE. Again, the result of this
experiment is reminiscent of the aforementioned fact that
(S)-28 is able to recognize (S)-2 in a more efficient and
rapid manner.
On the other hand, (R)-28 also tends to demonstrate
better chiral recognition of (R)-2. Thus, mixing of 1 molar
equiv of (R)-28 with 1.3 molar equiv of (R)-2 led to a
F IGURE 10. 1H NMR spectrum of the reaction mixtures of
1
mixture whose H NMR and 31P NMR spectra show new
(R)-28 and (R)-2 at a molar ratio of 1:1.3, and at the top right
corner of the spectrum is the corresponding 31P NMR spectrum.
peaks I, J , K, and PI, in addition to the original peaks H
and PH shown by (R)-28 (Figure 10), which are the same
as A and PA of (S)-28. These spectra are actually identical
to those obtained from reaction between (S)-2 and (S)-
28, i.e., Figure 7c. It is also clear from this result that
(R)-28 exhibits a tangible recognition of (R)-2. On the
contrary, the 1H NMR and 31P NMR spectroscopic results
obtained from the reaction between 1 molar equiv of (R)-
28 and 1.3 molar equiv of (S)-2 show new peaks L, M, N,
and PL, plus the original peaks H and PH from (R)-28
Figure 8a shows new peaks E, F, G, and PE, which do
not abate significantly even when the number of molar
equivalents of (R)-2 was increased from 1 to 1.8 (Figure
8b), indicating that the reaction is not complete even in
an excess of (R)-2. The result of the mixing of (S)-28 with
(R)-2 nonetheless confirms that a relatively slower reac-
tion has indeed taken place and that (S)-28 does not
recognize (R)-2 so easily.
8926 J . Org. Chem., Vol. 68, No. 23, 2003

1,16-Dihydroxytetraphenylene in Molecular Recognition and Assembly
under a positive pressure of argon. Dry freshly distilled
dioxane (70 mL) was syringed into the flask, and then
tetraethyl 1,1,2,2-ethanetetracarboxylate (8) (6.03 g, 19 mmol)
and freshly cut potassium (1.37 g, 34 mmol) were placed in
the reaction flask. After the reaction mixture was refluxed for
24 h, 2,2′-bis(bromomethyl)-6,6′-dimethoxybiphenyl (7) (5.00
g, 13 mmol) in dry dioxane (70 mL) was added dropwise slowly
into the yellow suspension via the dropping funnel. After the
addition was complete, the reaction mixture was refluxed for
an additional 48 h. The reaction was quenched with water (70
mL) and acidified with 2 M hydrochloric acid to a pH value of
3. The mixture was extracted with ethyl acetate (2 × 150 mL),
and the organic solution was washed with brine (2 × 100 mL)
and dried over anhydrous sodium sulfate. Removal of the
solvent and flash column chromatography on silica gel (pe-
troleum ether/ethyl acetate 5:1) gave 9 as a white solid (4.72
g, 68%), mp 99-102 °C. 1H NMR (300 MHz, CDCl3): δ 7.22
(t, 2H, J ) 8.0 Hz), 6.84 (d, 4H, J ) 8.0 Hz), 4.23-4.15 (m,
4H), 4.03-3.82 (m, 4H), 3.87 (d, 2H, J ) 14.3 Hz), 3.72 (s,
6H), 3.39 (d, 2H, J ) 14.4 Hz), 1.25 (t, 6H, J ) 7.1 Hz), 0.99
(t, 6H, J ) 7.2 Hz). 13C NMR (100.4 MHz, CDCl3): δ 169.8,
169.4, 157.3, 138.3, 127.7, 126.3, 123.1, 109.4, 62.9, 61.9, 61.1,
55.9, 36.6, 13.9, 13.4. MS (EI): m/z (relative intensity) 512
(100), 511 (96), 556 (M+, 89), 557 (55), 436 (54), 350 (47), 437
(31), 409 (28). IR (KBr disk): 2984, 2904, 2839, 1730 (br), 1262,
1206 (br), 1095, 1037, 773, 755, 732 cm-1. Anal. Calcd for
F IGURE 12. 1H NMR spectrum of the reaction mixtures of
(R)-28 and (()-2 at a molar ratio of 1:2.9, and at the top right
corner of the spectrum is the corresponding 31P NMR spectrum.
TABLE 1. Resu lts of Ch ir a l Recogn ition betw een 2 a n d
28
(S)-2
(R)-2
(S)-28
(R)-28
matched
mismatched
mismatched
matched
C
30H36O10: C, 64.74; H, 6.52. Found: C, 64.37; H, 6.47.
1,12-Dim e t h oxy-5,6,7,8-t e t r a h yd r od ib e n zo[a ,c]c y-
(Figure 11). From the peak heights of PH and PL, a
conclusion can be drawn that the chiral recognition
between (R)-28 and (S)-2 is not as effective as that
between (R)-28 and (R)-2. Finally, the reaction between
1 molar equiv of (R)-28 and 2.9 molar equiv of (()-2 led
to spectra showing peaks H, I, J , K, L, M, N, PH, PI, and
PL, with peaks I and PI being the more noticeable
absorptions (Figure 12), thereby showing a better chiral
recognition of (R)-2 by (R)-28. It is noteworthy that
Figures 11 and 12 are in fact “enantiomeric” to Figures
8b and 9, respectively. In conclusion, Table 1 depicts a
summary of results concerning the chiral recognition
between 2 and 28.
cloocta n d ien e-6,7-d ica r boxylica cid (14). To the mixture
of potassium hydroxide (25.9 g, 0.46 mol) and ethylene glycol
(120 mL) was added 9 (6.92 g, 12 mmol). The mixture was
refluxed for 10 h and then cooled to room temperature. After
being acidified to pH ) 1 with 6 M hydrochloric acid, the
solution was extracted with diethyl ether (3 × 100 mL) and
the combined ethereal layer was washed with brine (3 × 100
mL) and dried over anhydrous sodium sulfate. Removal of
ether gave the light yellow crude 14, which was washed with
a small amount of diethyl ether to give pure 14 as a white
powder (4.02 g, 91%), mp 204-206 °C. 1H NMR (300 MHz,
CD3COCD3): δ 7.40-7.34 (m, 2H), 7.09-7.06 (m, 2H), 6.96-
6.93 (m, 2H), 3.73-3.70 (m, 6H), 3.50 (br, 2H), 2.96-2.83 (m,
4H), 2.30-2.08 (m, 2H). 13C NMR (75.3 MHz, CD3COCD3): δ
177.1, 158.9, 142.7, 130.6, 126.9, 122.7, 110.6, 56.7, 49.8, 35.3.
MS (EI): m/z (relative intensity) 338 (100), 356 (M+, 39), 91
(29), 249 (26), 235 (23), 265 (19), 251 (18), 310 (17). IR (KBr
disk): 3100-2936 (br), 2835, 1699, 1584, 1464, 1436, 1263,
1074, 1085, 929, 790, 757, 736 cm-1. HRMS (M+): calcd for
Con clu sion
1,16-Dihydroxytetraphenylene (2) has been synthe-
sized with an approximate overall yield of 4% in eight
steps, featuring an unusual NBS bromination of 1,12-
dimethoxy-5,8-dihydrodibenzo[a,c]cyclooctene (10). The
enantiomers of 2 have also been obtained by a chromato-
graphic separation of the corresponding diastereomeric
bis(S)-camphorsulfonates, followed by a subsequent de-
sulfonation step. We have also been successful in obtain-
ing a bis-diphenylphosphine derivative of 2, namely,
(()-26, whose platinum complex 27 was also prepared
and characterized by X-ray crystallographic analysis. 4,4′-
Bipyridine was utilized to realize two hydrogen bonded
molecular complexes with (()-2 and (S)-2, whose crystal
packing patterns are very much different. Chiral recogni-
tion experiments have also been performed by reacting
2 with 28, and the spectroscopic results nevertheless
point to the likelihood that (S)-28 and (R)-28 would
recognize (S)-2 and (R)-2, respectively.
C
20H20O6 356.1260, found 356.1269.
1,12-Dim et h oxy-5,8-d ih yd r od ib en zo[a ,c]cyclooct en e
(10). To a mixture of lead tetraacetate (1.10 g, 2.37 mmol) and
14 (561 mg, 1.58 mmol) were added dry benzene (15 mL) and
dry pyridine (0.3 mL, 3.7 mmol). The reaction mixture was
stirred for 6 h at 80 °C. The dark mixture was filtered through
a sintered glass funnel padded with a layer of silica gel, and
the filter cake was washed thoroughly with benzene. The
filtrate was washed sequentially with 2 M hydrochloric acid
(2 × 25 mL) and water (2 × 25 mL). The benzene solution
was dried with anhydrous sodium sulfate. Removal of the
solvent and flash column chromatography on silica gel (pe-
troleum ether/ethyl acetate 50:1) gave 10 as a white solid (140
mg, 33%), mp 142-143 °C. 1H NMR (300 MHz, CDCl3): δ 7.30
(t, 2H, J ) 7.9 Hz), 6.84 (d, 4H, J ) 7.9 Hz), 5.81-5.78 (m,
2H), 3.75 (s, 6H), 3.11-3.03 (m, 2H), 2.91 (d, 2H, J ) 13.8
Hz). MS (EI): m/z (relative intensity) 266 (M+, 100), 235 (59),
251 (19), 220 (19), 203 (16), 205 (16), 165 (15), 219 (15). IR
(KBr disk): 3059, 3020, 2934, 2841, 1643, 1577, 1467, 1456,
1435, 1257, 1086, 1075, 768, 752, 730 cm-1. Anal. Calcd for
Exp er im en ta l Section
C
18H18O2: C, 81.17; H, 6.81. Found: C, 80.98; H, 6.90.
Tetr a eth yl 1,12-Dim eth oxy-5,6,7,8-tetr a h yd r od iben zo-
[a ,c]cyclooct en e-6,6,7,7-t et r a ca r b oxyla t e (9). A dry 250
mL round-bottomed flask fitted with a condenser and a
dropping funnel was charged with dry argon and maintained
1,12-Dim eth oxy-6,7-d ibr om o-5,6,7,8-tetr a h yd r od iben -
zo[a ,c]cycloocten e (15). To a solution of 10 (204 mg, 0.77
mmol) in carbon tetrachloride (4 mL) was added dropwise 0.54
M bromine in carbon tetrachloride (1.5 mL, 0.81 mmol) at
J . Org. Chem, Vol. 68, No. 23, 2003 8927

Wen et al.
ambient temperature. After the addition was complete, the
orange solution was stirred for 8 h at room temperature. After
the solvent was removed on a rotary evaporator, the residual
crude product was washed with a small amount of diethyl
ether to supply 15 as a white solid (310 mg, 95%). 1H NMR
(300 MHz, CDCl3): δ 7.34 (t, 2H, J ) 7.9 Hz), 7.03 (d, 2H, J
) 7.3 Hz), 6.91 (dd, 2H, J ) 8.2, 0.6 Hz), 4.31-4.35 (m, 2H),
3.74 (s, 6H), 3.36 (dd, 2H, J ) 13.9, 1.2 Hz), 2.84-2.93 (m,
2H). MS (EI): m/z (relative intensity) 265 (100), 426 (M+, 48),
250 (36), 266 (36), 235 (27), 424 (25), 428 (25), 234 (24). HRMS
(M+): calcd for C18H18Br2O2 423.9674, found 423.9683.
1,12-Dim et h oxyd ib en zo[a ,c]cyclooct en e (16). Dibro-
mide 15 (211 mg, 0.50 mmol) was dissolved in dry benzene (7
mL), and 1,5-diazabicyclo[4.3.0]non-5-ene (DBN) (0.4 mL, 3
mmol) was added by a syringe. The reaction mixture was
refluxed for 15 h and allowed to cool. The solution was treated
successfully with 10% sulfuric acid (5 mL), water (2 × 10 mL),
and brine (20 mL) and then dried over anhydrous sodium
sulfate. Removal of the solvent and flash column chromatog-
raphy on silica gel (petroleum ether/ethyl acetate 20:1) gave
16 (38 mg, 29%), which was difficult to obtain in a sufficiently
pure form for proton NMR spectroscopy but was characterized
by HRMS and X-ray diffraction. HRMS (MNa+): calcd for
ture. The reaction mixture was quenched with water (30 mL).
After most of the THF was removed on a rotary evaporator,
the residual solution was extracted with ethyl acetate (2 × 50
mL). The organic layer was washed with water (30 mL) and
dried over anhydrous sodium sulfate. Removal of the solvent
and flash column chromatography on silica gel (petroleum
ether/ethyl acetate 2:1) provided 12 as a yellow powder (920
mg, 61%), which was a mixture of several isomers and used
in the next step without further purifcation. 1H NMR (300
MHz, CDCl3): δ 7.44-6.40 (m, 10H), 5.78-5.22 (m, 4H), 3.68-
3.52 (m, 6H). MS (EI): m/z (relative intensity) 69 (100), 226
(99), 131 (70), 239 (63), 329 (63), 270 (60), 293 (52), 294 (52).
IR (KBr disk): 2998, 2835, 1733, 1573, 1459, 1428, 1254, 1128,
1115, 1074, 1028, 1017, 1028, 1017, 878, 823, 797, 787, 731,
703 cm-1
.
1,16-Dim eth oxytetr a p h en ylen e (13). To dry THF (15
mL) was added dropwise titanium tetrachloride (2.5 mL, 23
mmol) at -78 °C, followed by lithium aluminum hydride (451
mg, 12 mmol) and triethylamine (4.5 mL, 32 mmol). The dark
mixture was refluxed for 0.5 h and then cooled to room
temperature. Compound 12 (910 mg, 2.3 mmol) in dry THF
(25 mL) was added into the reaction flask via a dropping
funnel. After the addition was complete, the reaction mixture
was stirred for 39 h at ambient temperature. The reaction was
quenched by carefully adding water (10 mL) and 6 M hydro-
chloric acid (5 mL). After most of the THF was removed on a
rotary evaporator, the residual mixture was extracted with
ethyl acetate (2 × 20 mL). The combined organic extract was
washed with water (2 × 20 mL) and dried over anhydrous
sodium sulfate. Removal of the solvent on a rotary evaporator
and flash column chromatography on silica gel (petroleum
ether/dichloromethane 2:1) gave 13 as a white solid (668 mg,
80%), mp 185-195 °C (sublimed). 1H NMR (300 MHz,
CDCl3): δ 7.27-7.18 (m, 8H), 7.13-7.10 (m, 2H), 6.79 (td, 4H,
J ) 8.5, 0.6 Hz), 3.68 (s, 6H). 13C NMR (75.3 MHz, CDCl3): δ
156.8, 143.3, 141.8, 141.5, 128.8, 128.2, 128.1, 127.1, 127.1,
126.3, 121.8, 110.2, 56.3. MS (EI): m/z (relative intensity) 364
(M+, 100), 86 (83), 365 (29), 57 (28), 55 (25), 289 (21), 145 (16),
144 (14). IR (KBr disk): 3057, 2988, 2930, 2829, 1577, 1462,
1423, 1351, 1261, 1125, 1025, 865, 791, 761, 752, 734, 659,
558, 516 cm-1. Anal. Calcd for C26H20O2: C, 85.69; H, 5.53.
Found: C, 85.61; H, 5.64.
1,16-Dih yd r oxytetr a p h en ylen e (2). To a solution of 13
(662 mg, 1.8 mmol) in dry dichloromethane (25 mL) was added
1 M boron tribromide in dichloromethane (10 mL, 10 mmol)
via a dropping funnel at 0 °C. The reaction mixture was stirred
for 18 h at ambient temperature. The reaction mixture was
treated successively with 6 M hydrochloric acid (10 mL) and
water (10 mL) and then extracted with dichloromethane (2 ×
50 mL). The organic phase was dried over anhydrous sodium
sulfate. Removal of the solvent and flash column chromatog-
raphy on silica gel (petroleum ether/ethyl acetate 2:1) gave 2
as a white solid (595 mg, 97%), mp 200-220 °C (sublimed).
1H NMR (300 MHz, CD3COCD3): δ 7.36-7.22 (m, 6H), 7.11-
7.03 (m, 4H), 6.77 (dd, 2H, J ) 8.1, 1.2 Hz), 6.61 (dd, 2H, J )
7.2, 1.2 Hz). MS (EI): m/z (relative intensity) 336 (M+, 100),
289 (21), 337 (17), 307 (16), 308 (16), 40 (14), 145 (13), 144
(11). IR (KBr disk): 3499 (br), 1572, 1453, 1452, 1187, 1177,
1158, 1006, 901, 797, 761, 751, 738 cm-1. Anal. Calcd for
C
18H16O2Na 287.1043, found 287.1049.
1,12-Dim eth oxy-5,6,7-tr ibr om o-5,6-dih ydr odiben zo[a ,c]-
cycloocten e (18). To dry carbon tetrachloride (20 mL) were
added 10 (146 mg, 0.55 mmol), N-bromosuccinimide (308 mg,
1.7 mmol), and benzoyl peroxide (11 mg, 0.05 mmol). The
reaction mixture was refluxed for 10 h until the complete
formation of succinimide floating upon the surface of carbon
tetrachloride was evident. The succinimide was filtered off and
washed thoroughly with carbon tetrachloride. After removal
of the solvent, the mixture was solidified in n-hexane and
washed with a minimum amount of diethyl ether to give 18
as a white solid (216 mg, 78%), which was directly used in the
next step. Purification by flash column chromatography on
silica gel (petroleum ether/ethyl acetate 20:1) gave a pure
sample of 18 for characterization, mp 180-198 °C (sublimed).
1H NMR (300 MHz, CDCl3): δ 7.39-7.49 (m, 3H), 6.81-7.02
(m, 3H), 6.85 (s, 1H), 5.20 (d, 1H, J ) 11.1 Hz), 4.95 (d, 1H, J
) 10.8 Hz), 3.80 (s, 3H), 3.77 (s, 3H). MS (EI): m/z (relative
intensity) 263 (100), 262 (72), 189 (55), 232 (53), 264 (41), 233
(36), 343 (29), 248 (29). IR (KBr disk): 3050, 2999, 2930, 2834,
1573, 1461, 1265, 1099, 1076, 777, 753, 730 cm-1. Anal. Calcd
for C18H15Br3O2: C, 42.98; H, 3.00. Found: C, 43.15; H, 3.19.
1,12-Dim et h oxy-6,7-d ib r om od ib en zo[a ,c]cyclooct en e
(11). To 18 (722 mg, 1.4 mmol) was added dry benzene (30
mL) by a syringe and then 1,5-diazabicyclo[4.3.0]non-5-ene
(DBN) (1.8 mL, 14 mmol). The reaction mixture was refluxed
for 12 h, allowed to cool, and washed successively with 2 M
hydrochloric acid (2 × 30 mL) and brine (4 × 50 mL). The
benzene solution was dried over anhydrous sodium sulfate.
Removal of the solvent on a rotary evaporator and flash column
chromatography on silica gel (petroleum ether/dichloromethane
3:1) gave 11 as a white solid (368 mg, 61%), mp 200-220 °C
(sublimed). 1H NMR (300 MHz, CDCl3): δ 7.30 (t, 2H, J ) 8.0
Hz), 7.06 (s, 2H), 6.88 (d, 2H, J ) 8.1 Hz), 6.80 (d, 2H, J ) 7.8
Hz), 3.68 (s, 6H). 13C NMR (75.3 MHz, CDCl3): δ 157.8, 138.1,
136.3, 128.4, 125.5, 121.0, 120.0, 110.4, 56.1. MS (EI): m/z
(relative intensity) 262 (100), 342 (39), 263 (38), 341 (38), 310
(31), 312 (31), 189 (28), 343 (28). IR (KBr disk): 3059, 3012,
2940, 2837, 1602, 1575, 1489, 1461, 1431, 1303, 1259, 1081,
C
24H16O2: C, 85.69; H, 4.79. Found: C, 85.44; H, 4.95.
(S )-(+)-1,16-Bis[(S )-ca m p h or su lfon yloxy]t e t r a p h e -
n ylen e (19) a n d (R)-(+)-1,16-Bis[(S)-ca m p h or su lfon yloxy]-
tetr a p h en ylen e (20). To a solution of (()-2 (299 mg, 0.89
mmol) and (S)-(+)-camphorsulfonyl chloride (97% ee, 2.31 g,
9.2 mmol) in THF (30 mL) was added dropwise triethylamine
(1.3 mL, 9.3 mmol) at 0 °C. The resulting mixture was stirred
for 42 h at room temperature until TLC indicated complete
consumption of (()-2. After most of the THF was removed on
a rotary evaporator, the residue was treated with water (10
mL) and extracted with dichloromethane (2 × 20 mL). The
organic solution was dried over anhydrous sodium sulfate.
Removal of the solvent and flash column chromatograph on
867, 856, 781, 756, 731, 657 cm-1. Anal. Calcd for C18H14
Br2O2: C, 51.22; H, 3.34. Found: C, 51.43; H, 3.39.
-
1,4:5,8-Diep oxy-12,13-d im eth oxy-1,4,5,8-tetr a h yd r otet-
r a p h en ylen e (12). To a solution of 11 (1.61 g, 3.8 mmol) in
dry THF (10 mL) was added furan (15 mL, freshly distilled
from sodium wire). A solution of potassium tert-butoxide (1.72
g, 15 mmol) in dry THF (25 mL) was added slowly into the
reaction mixture via
a dropping funnel under an argon
atmosphere. After the addition was complete, the yellowish
green suspension was stirred for 130 h at ambient tempera-
8928 J . Org. Chem., Vol. 68, No. 23, 2003

1,16-Dihydroxytetraphenylene in Molecular Recognition and Assembly
Hz), 7.36-7.23 (m, 10H), 7.17-7.14 (m, 2H). 13C NMR (75.3
silica gel (petroleum ether/ethyl acetate 6:1) yielded the crude
product containing the two diastereomeric bissulfonates 19 and
20 in almost quantitative yield, which could be separated by
repeated flash column chromatography with benzene and ethyl
acetate (20:1) as the eluent followed by recrystallization from
CH3OH-CH2Cl2. Both diastereomeric bissulfonates 19 and 20
were obtained in over 94% (97.9% ee) and 97% (97.5% ee)
yields, respectively. Single crystals of the less polar bissul-
fonate 19 were grown from CH3OH, and its (S)-configuration
was determined on the basis of an X-ray diffraction analysis.
Da ta of 19, mp 239-240 °C. [R]20D: +47.4 (c ) 1.0, CH2Cl2).
1H NMR (300 MHz, CDCl3): δ 7.41-7.27 (m, 10H), 7.22-7.13
(m, 4H), 3.20 (d, 2H, J ) 15.3 Hz), 3.00 (d, 2H, J ) 14.7 Hz),
2.42-2.34 (m, 4H), 2.13-2.00 (m, 4H), 1.95 (d, 2H, J ) 18.6
Hz), 1.61-1.38 (m, 4H), 1.09 (s, 6H), 0.85 (s, 6H). MS (EI):
m/z (relative intensity) 337 (100), 336 (96), 215 (77), 551 (59),
260 (49), 151 (49), 109 (48), 259 (47). IR (KBr disk): 3063, 2960,
1750 (vs), 1572, 1453, 1433, 1424, 1365, 1224, 1176, 1164,
1080, 1049, 912, 799, 761, 748, 576, 557, 513, 501 cm-1. Anal.
Calcd for C24H44O2: C, 69.09; H, 5.80. Found: C, 69.01; H,
5.95. Da ta of 20, mp 206-207 °C. [R]20D: +3.4 (c ) 1.4, CH2-
Cl2). 1H NMR (300 MHz, CDCl3): δ 7.47-7.25 (m, 10H), 7.21-
7.11 (m, 4H), 3.54 (d, 2H, J ) 15.0 Hz), 2.81 (d, 2H, J ) 15.3
Hz), 2.42-2.33 (m, 2H), 2.21-1.97 (m, 6H), 1.92 (d, 2H, J )
18.6 Hz), 1.64-1.55 (m, 2H), 1.45-1.36 (m, 2H), 0.97 (s, 6H),
0.79 (s, 6H). Anal. Calcd for C24H16O2: C, 69.09; H, 5.80.
Found: C, 69.13; H, 6.01.
(S)-(+)-1,16-Dih yd r oxytetr a p h en ylen e ((S)-2). To a so-
lution of 19 (141 mg, 0.18 mmol) in methanol (10 mL) and
water (2 mL) was added potassium hydroxide (288 mg, 5.1
mmol). The reaction mixture was refluxed for 5 h and then
allowed to cool. After most of the methanol was removed on a
rotary evaporator, the residue mixture was acidified with 2
M hydrochloric acid to pH ) 1 and then extracted with
dichloromethane (2 × 20 mL). The organic layer was washed
with brine (3 × 20 mL) and dried over anhydrous sodium
sulfate. Removal of the solvent and flash column chromatog-
raphy on silica gel (petroleum ether/ethyl acetate 2:1) gave
(S)-2 as a white solid (63 mg, 100%), with 97% purity and
99.3% ee as determined by chiral HPLC. The spectroscopic
data of (S)-2 were identical to those of (()-2. [R]20D: +66.2 (c
) 1.0, CH2Cl2).
(R)-(-)-1,16-Dih yd r oxytetr a p h en ylen e ((R)-2). To a so-
lution of 20 (155 mg, 0.20 mmol) in methanol (10 mL) and
water (2 mL) was added potassium hydroxide (261 mg, 4.7
mmol). The reaction mixture was refluxed for 5 h and then
allowed to cool. After most of the methanol was removed on a
rotary evaporator, the residue was acidified with 2 M hydro-
chloric acid to pH ) 1 and then extracted with dichlo-
romethane (2 × 20 mL). The organic layer was washed with
brine (3 × 20 mL) and dried over anhydrous sodium sulfate.
Removal of the solvent and flash column chromatography on
silica gel (petroleum ether/ethyl acetate 2:1) gave (R)-2 as a
white solid (69 mg, 100%), with a purity of 95% and 99.4% ee
as determined by chiral HPLC. The spectroscopic data of (R)-2
were identical to those of (()-2. [R]20D: -61.4 (c ) 1.0, CH2-
Cl2).
1,16-Bis(t r iflu or om et h a n esu lfon yloxy)t et r a p h en yl-
en e (21). To a solution of 1,16-dihydroxytetraphenylene (2)
(116 mg, 0.35 mmol) in dry dichloromethane (15 mL) was
added pyridine (1.5 mL, 13 mmol) and then trifluoromethane
sulfonic anhydride (1.5 mL, 9.1 mmol) at 0 °C. After the
addition, the reaction mixture was stirred for 69 h at ambient
temperature. When TLC indicated the reaction was complete,
water (5 mL) was added carefully. The mixture was extracted
with dichloromethane (2 × 15 mL). The organic layer was
washed sequentially with 1 M hydrochloric acid (10 mL) and
brine (2 × 20 mL), dried over anhydrous sodium sulfate.
Removal of the solvent on a rotary evaporator and flash column
chromatography on silica gel (petroleum ether/ethyl acetate
50:1) gave 21 as a white solid (202 mg, 98%), mp 210-220 °C
(sublimed). 1H NMR (300 MHz, CDCl3): δ 7.44 (t, 2H, J ) 8.1
MHz, CDCl3): δ 145.9, 145.6, 140.5, 138.7, 130.3, 129.8, 129.5,
129.0, 128.2, 127.8, 127.3, 120.2, 120.1, 115.9. MS (EI): m/z
(relative intensity) 299 (100), 600 (M+, 38), 306 (37), 289 (27),
300 (24), 305 (23), 105 (21), 276 (20). IR (KBr disk): 1460, 1423
(vs), 1251, 1220 (vs), 1142 (vs), 1075, 920, 908, 809, 763, 751,
604, 513 cm-1. Anal. Calcd for C26H14O6S2F6: C, 52.00; H, 2.35.
Found: C, 51.78; H, 2.40.
1-(Dip h en ylp h osp h in yl)-16-(t r iflu or om et h a n esu lfo-
n yloxy)tetr a p h en ylen e (22). To a mixture of 21 (61 mg, 0.10
mmol), diphenylphosphine oxide (60 mg, 0.30 mmol), pal-
ladium acetate (8 mg, 0.035 mmol), and 1,4-bis(diphenylphos-
phino)butane (dppb) (16 mg, 0.038 mmol) were added dry
dimethyl sulfoxide (7 mL) and diisopropylethylamine (60 µL,
0.32 mmol). The mixture was heated with stirring at 100 °C
for 24 h. After being cooled to room temperature, the reaction
mixture was concentrated under reduced pressure (0.1 mmHg)
to give a dark brown residue, which was diluted with ethyl
acetate (25 mL). The ethyl acetate solution was washed with
water (15 mL) and dried over anhydrous sodium sulfate.
Removal of the solvent and flash column chromatography on
silica gel (petroleum ether/ethyl acetate 2:1) provided 22 as a
white solid (63 mg, 97%), mp 134-136 °C. 1H NMR (300 MHz,
CDCl3): δ 7.64-7.03 (m, 23H), 6.80 (d, 1H, J ) 7.2 Hz). 13C
NMR (75.3 MHz, CDCl3): δ 147.1, 144.8, 144.6, 143.9, 141.0,
140.9, 140.0, 139.8, 137.9, 137.8, 134.3, 133.6, 133.1, 133.1,
132.9, 132.7, 132.2, 132.2, 132.1, 132.1, 131.9, 131.9, 131.8,
131.6, 131.5, 131.3, 131.3, 130.7, 129.4, 129.4, 128.7, 128.6,
128.3, 128.3, 128.2, 128.2, 128.0, 127.9, 127.8, 127.5, 127.4,
127.4, 127.3, 127.2, 124.5, 120.2, 119.4, 116.0, 111.8. 31P NMR
(121.5 MHz, CDCl3): δ 30.2. MS (ESI): m/z 653 (MH+, 100),
675 (MNa+, 28). IR (KBr disk): 3010, 1452, 1436, 1404 (vs),
1250, 1221 (vs), 1204 (vs), 1160, 1143 (vs), 1118, 1068, 917,
904, 812, 750, 696, 603, 533 (vs) cm-1. HRMS (MNa+): calcd
for C37H24F3O4PSNa 675.0977, found 675.0999.
1-(Dip h e n ylp h osp h in o)-16-(t r iflu or om e t h a n e su lfo-
n yloxy)tetr a p h en ylen e (23). Under a dry argon atmosphere,
22 (77 mg, 0.12 mmol), dry toluene (8 mL), dry triethylamine
(2 mL, 14 mmol), and trichlorosilane (∼1.5 mL, 15 mmol) were
added sequentially into a 20 mL sealed tube with a Teflon
screwcap cooled at 0 °C. The reaction mixture was stirred for
28 h at 120 °C in the sealed tube. After cooling to the room
temperature, the reaction mixture was transferred to a 100
mL beaker and diluted with diethyl ether (100 mL). Addition
of water resulted in a sticky suspension, which was filtered
through a sintered glass funnel padded with silica gel. The
organic phase was separated, washed with brine (3 × 50 mL),
and then dried over anhydrous sodium sulfate. Removal of the
solvent and flash column chromatography on silica gel (pe-
troleum ether/ethyl acetate 50:1) gave 23 as a white solid (66
mg, 89%), with the recovery of the precursor 22 (10 mg).
Compound 23 must be kept in an atmosphere of argon due to
its instability in air. 1H NMR (300 MHz, CDCl3): δ 7.39-6.97
(m, 20H), 6.89 (t, 1H, J ) 7.5 Hz), 6.79 (t, 2H, J ) 7.5 Hz),
6.06 (d, 1H, J ) 7.5 Hz). 13C NMR (75.3 MHz, CDCl3): δ 145.8,
143.2, 141.1, 140.8, 140.6, 139.2, 137.4, 137.3, 137.1, 135.2,
134.4, 134.1, 133.1, 133.0, 132.8, 130.6, 129.6, 129.3, 128.8,
128.7, 128.6, 128.6, 128.5, 128.5, 128.4, 128.4, 128.3, 128.2,
128.0, 127.5, 127.4, 127.2, 127.0, 120.1. 31P NMR (121.5 MHz,
CDCl3): δ -12.7. MS (ESI): m/z 637 (MH+, 66). IR (KBr
disk): 3400 (br), 3061, 2963, 2923, 2852, 1434, 1421, 1248,
1212, 1159, 1143, 921, 909, 829, 805, 745, 696, 601 cm-1
.
HRMS (MH+): calcd for C37H25F3O3PS 637.1209, found
637.1206.
1,16-Bis(d ip h en ylp h osp h in yl)tetr a p h en ylen e (25). To
a mixture of diphenylphosphine oxide (167 mg, 0.83 mmol) and
1,4-diazabicyclo[2.2.2]octane (DABCO) (133 mg, 1.0 mmol) was
added N,N-dimethylacetamide (8 mL). The solution was de-
gassed under vacuum and argon seven times and then charged
with [1,2-bis(diphenylphosphino)ethane] nickel(II) chloride
(NiCl2‚dppe, 22 mg, 0.024 mmol) and 23 (45 mg, 0.07 mmol).
The reaction mixture was heated to 100 °C and stirred for
J . Org. Chem, Vol. 68, No. 23, 2003 8929

Wen et al.
about 50 h at this temperature until the reaction solution
became clear. The reaction mixture was allowed to cool, and
N,N-dimethylacetamide was removed under reduced pressure
(about 0.2 mmHg). The residue was diluted with ethyl acetate
(15 mL), and the insoluble solid was removed by filtration.
Removal of the solvent and flash column chromatography on
silica gel (petroleum ether/ethyl acetate 1:1) gave 25 as a white
solid (9 mg, 18%) and 1-diphenylphosphinyltetraphenylene
(24) as a byproduct (20 mg, 56%). Da ta of 25, mp > 320 °C.
1H NMR (300 MHz, CDCl3): δ 7.84-7.77 (m, 4H), 7.56-6.91
(m, 26H), 6.73 (td, 2H, J ) 7.5, 1.4 Hz), 6.11 (dd, 2H, J ) 7.5,
0.9 Hz). 13C NMR (75.3 MHz, CDCl3): δ 141.3, 140.9, 132.9,
132.7, 132.6, 132.5, 132.2, 131.6, 131.5, 131.4, 131.0, 130.9,
128.4, 128.3, 128.1, 128.1, 127.3, 127.0, 126.6, 126.5. 31P NMR
(121.5 MHz, CDCl3): δ 28.7. MS (ESI): m/z 705 (MH+, 100).
IR (KBr disk): 3400 (br), 3051, 2923, 2852, 1647 (br), 1436
(vs), 1400 (m), 1210 (vs), 1195 (vs), 1147, 1116-1028 (br, vs),
748, 721, 696 (vs), 545 (vs), 532 (vs), 481 cm-1. HRMS (MH+):
calcd for C48H35O2P2 705.2107, found 705.2124. Da ta of 24.
1H NMR (300 MHz, CDCl3): δ 7.66-6.95 (m, 23H), 6.70-6.64
(m, 2H). 13C NMR (75.3 MHz, CDCl3): δ 145.2, 145.1, 144.3,
144.2, 141.6, 141.5, 141.5, 141.2, 141.2, 141.2, 141.1, 141.1,
141.1, 137.5, 137.4, 137.4, 134.3, 134.3, 134.2, 133.8, 133.7,
133.6, 133.3, 133.3, 133.0, 132.8, 132.8, 132.4, 132.3, 132.2,
132.1, 131.6, 131.5, 131.5, 131.4, 131.3, 131.1, 131.0, 130.8,
129.2, 129.1, 128.8, 128.8, 128.6, 128.6, 128.4, 128.4, 128.3,
128.3, 128.0, 127.7, 127.5, 127.4, 127.1, 127.0, 126.9, 126.3.
MS (ESI): m/z 505 (MH+, 100), 1031 (2M+Na+, 34). HRMS
(MNa+): calcd for C36H25OPNa 527.1535, found 527.1532.
(integration values indicate the formation of molecular complex
with a molar ratio of 1:2).
(S)-BINAP -P tCO3 ((S)-28). A mixture of (S)-BINAP-
PtCl2 (102 mg, 0.12 mmol) and silver carbonate (72 mg, 0.26
mmol) in wet dichloromethane (saturated in water, 30 mL)
was stirred under darkness for 4.5 h. The insoluble solid was
filtered, and the solvent was removed on a rotary evaporator
to give (S)-28 (97 mg, 96%). 1H NMR (300 MHz, CDCl3): δ
7.93-7.86 (m, 4H), 7.59-7.38 (m, 16H), 7.23-7.09 (m, 4H),
6.92 (d, 2H, J ) 5.7 Hz), 6.80 (d, 2H, J ) 6.9 Hz), 6.64-6.59
(m, 4H). 31P NMR (121.5 MHz, CDCl3): δ 4.85 (J P-Pt ) 3648
Hz).
(R)-BINAP -P tCO3 ((R)-28). The procedure for the prepa-
ration of (R)-28 was similar to that for (S)-28. The spectro-
scopic data of (R)-28 were identical with those of (S)-28.
Rea ction betw een (S)-28 a n d (S)-2. Under an argon
atmosphere, (S)-28 (12 mg, 0.014 mmol), (S)-2 (4 mg, 0.013
mmol), and dry CDCl3 (0.5 mL) were added into a NMR tube.
The yellowish green clear solution was treated with supersonic
1
waves for 20 min and then characterized by H NMR and 31P
NMR spectroscopy. In view of the complication of the proton
NMR spectra, only characteristic peaks discussed in the article
are reported (parts per million, peak multiplicities, relative
1
integration, and coupling constant (Hz)). H NMR (300 MHz,
CDCl3): δ 7.92-7.85 (m, 2.15), 7.83-7.76 (m, 4.18), 6.51 (d,
2.15, J ) 7.2 Hz), 6.30 (d, 2.0, J ) 7.2 Hz) (the peak between
7.92 and 7.85 ppm almost completely disappeared when (S)-2
was increased to 1.6 molar equiv). 31P NMR (121.5 MHz,
CDCl3): δ 5.76 (s, 1.0), 4.79 (s, 0.5) (1.0 and 0.5 are the relative
integration values of the two peaks; the peak at 4.79 ppm
almost completely disappeared when (S)-2 was increased to
1.6 molar equiv). HRMS (MNa+): calcd for C68H46O2P2190PtNa
1169.2465, found 1169.2475.
1,16-Bis(d ip h en ylp h osp h in o)tetr a p h en ylen e (26). In a
20 mL tube sealed with a Teflon screwcap was placed 25 (14
mg, 0.02 mmol), dry toluene (5 mL), and dry triethylamine (2
mL, 14 mmol). Trichlorosilane (∼1.5 mL, 14 mmol) was added
into the tube at 0 °C. The reaction mixture was kept at 120
°C in the sealed tube for 42 h. After cooling to room temper-
ature, the reaction mixture was transferred to a 50 mL beaker
and diluted with toluene (20 mL). Aqueous sodium hydroxide
(10 M) was added to quench the reaction until the organic and
aqueous layers became clear. The organic layer was separated,
and the aqueous layer was extracted with warm toluene (2 ×
20 mL). The combined organic layer was washed with 2 M
hydrochloric acid (15 mL), saturated aqueous sodium hydrogen
carbonate (20 mL), and brine (2 × 20 mL) and then dried over
anhydrous sodium sulfate. Removal of the solvent gave the
crude 26 as a yellow solid. Further purification by washing
26 with a minimum amount of toluene (2 × 0.5 mL) gave 26
as a white solid (8 mg, 60%). Due to its potential instability
in air, compound 26 was used immediately in the next step
after being characterized by 31P NMR. 31P NMR (121.5 MHz,
C6D6): δ -11.5.
Rea ction betw een (S)-28 a n d (S)-2 a t a n Equ a l Mola r
Ra tio in Reflu xin g CHCl3. To a mixture of (S)-28 (27 mg,
0.03 mmol) and (S)-2 (10 mg, 0.03 mmol) was added dry
chloroform (1 mL). The clear greenish solution was refluxed
for 15 h. After removal of the solvent under reduced pressure,
the residual yellow powder was dried in a vacuum at 70 °C.
After 45 min, the powder was dissolved in dry CDCl3 for the
1
study of NMR. H NMR (300 MHz, CDCl3): δ 7.91-7.85 (m,
4H), 7.66-7.61 (m, 4H), 7.53 (d, 2H, J ) 6.9 Hz), 7.40-7.05
(m, 22H), 6.83-6.63 (m, 10H), 6.49 (d, 2H, J ) 7.2 Hz), 6.34
(d, 2H, J ) 8.1 Hz). 31P NMR (121.5 MHz, CDCl3): δ 5.52.
1
Rea ction betw een (S)-28 a n d (R)-2. H NMR (300 MHz,
CDCl3): δ 8.09-8.03 (m, 3.8), 7.91-7.84 (m, 2.14), 6.49 (d, J
) 6.9 Hz), 5.91 (d, 2.0, J ) 7.2 Hz) (the peak between 7.91
and 7.84 ppm diminished apparently when (S)-2 was increased
to 1.8 molar equiv). 31P NMR (121.5 MHz, CDCl3): δ 5.55 (s,
1.0), 4.77 (s, 0.5) (1.0 and 0.5 are the relative integration values
of the two peaks, and the two values changed to 1.0 and 0.3
when (S)-2 was increased to 1.8 molar equiv).
BP TP -P tCl2 (27). A mixture of dichloro(1,5-cyclooctadi-
ene)platinium (4.70 mg, 0.01 mmol) and 26 (8.00 mg, 0.01
mmol) in dichloromethane (2 mL) was stirred for 10 h at room
temperature. After removal of the solvent, the residual powder
was dried in a vacuum at 65 °C to give 27 (9.1 mg, 81%). Its
structure was determined on the basis of X-ray diffraction
analysis of a crystalline sample grown from dichloromethane.
31P NMR (121.5 MHz, CD2Cl2): δ +10.6.
1
Rea ction betw een (S)-28 a n d (()-2. H NMR (300 MHz,
CDCl3): δ 8.03-7.97 (m, 2.1), 7.76-7.70 (m, 4.8), 6.53 (d, J )
7.2 Hz), 6.50 (d, J ) 7.5 Hz), 6.33 (d, 2.0, J ) 7.8 Hz), 5.88 (d,
J ) 7.2 Hz). 31P NMR (121.5 MHz, CDCl3): δ 5.47 (s, 1.0),
4.86 (s, 1.89) (1.0 and 1.89 are the relative integration values
of the two peaks).
Rea ction betw een (R)-28 a n d (R)-2. 1H NMR (300 MHz,
CDCl3): δ 7.91-7.85 (m, 1.5), 7.82-7.77 (m, 4.5), 6.46 (d, 2.2,
J ) 7.5 Hz), 6.29 (d, 2, J ) 7.8 Hz) (the peak between 7.91
and 7.85 ppm almost completely disappeared when (R)-2 was
increased to 2.0 molar equiv). 31P NMR (121.5 MHz, CDCl3):
δ 5.56 (s, 2.4), 4.81 (s, 1.0) (2.4 and 1.0 are the relative
integration values of the two peaks; the peak at 4.81 ppm
almost completely disappeared when (R)-2 was increased to
2.0 molar equiv).
Assem bly betw een 2 a n d 4,4′-Bip yr id in e. DHTP 2 [(()-
2 or (S)-2] (1 molar equiv) and 4,4′-bipyridine (2 molar equiv)
was dissolved in the solvent. The solvent was evaporated
slowly at room temperature to afford crystal for the studies of
proton NMR and X-ray diffraction. Da ta for (()-2 a n d 4,4′-
1
bip yr id in e. H NMR (300 MHz, CDCl3): δ 8.71 (dd, 4H, J )
4.5, 1.5 Hz), 7.55 (dd, 4H, J ) 4.5, 1.5 Hz), 7.29-7.10 (m, 10H),
6.90 (d, 2H, J ) 8.4 Hz), 6.82 (d, 2H, J ) 7.8 Hz), 5.56 (br)
(integration values indicate the formation of molecular complex
with a molar ratio of 1:1). Da ta for (S)-2 a n d 4,4′-bip yr id in e.
1H NMR (300 MHz, CDCl3): δ 8.71 (dd, 2 × 4H, J ) 4.5, 1.5
Hz), 7.55 (dd, 2 × 4H, J ) 4.5, 1.5 Hz), 7.29-7.10 (m, 10H),
6.88 (d, 2H, J ) 8.4 Hz), 6.78 (d, 2H, J ) 7.8 Hz), 5.56 (br)
1
Rea ction betw een (R)-28 a n d (S)-2. H NMR (300 MHz,
CDCl3): δ 8.08-8.01 (m, 2.0), 7.90-7.83 (m, 0.9), 6.48 (d, J )
7.5 Hz), 5.91 (d, 1.0, J ) 7.8 Hz). 31P NMR (121.5 MHz,
CDCl3): δ 5.56 (s, 2.0), 4.75 (s, 1.0) (2.0 and 1.0 are the relative
integration values of the two peaks).
8930 J . Org. Chem., Vol. 68, No. 23, 2003

1,16-Dihydroxytetraphenylene in Molecular Recognition and Assembly
Rea ction betw een (R)-28 a n d (()-2. 1H NMR (300 MHz,
CDCl3): δ 7.99-7.93 (m, 1.0), 7.73-7.67 (m, 2.7), 6.53 (d, J )
7.8 Hz), 6.44 (d, J ) 7.2 Hz), 6.34 (d, J ) 7.8 Hz), 5.85 (d, J )
7.8 Hz). 31P NMR (121.5 MHz, CDCl3): δ 5.34 (s, 1.0), 4.76 (s,
2.2) (1.0 and 2.2 are the relative integration values of the two
peaks).
Cr ysta llogr a p h ic Deta ils. All structures were solved by
direct methods (SHELXS-97) (Sheldrick, G. M. SHELX-97
Programs for Crystal Structure Analysis; University of Go¨t-
tingen: Go¨ttingen, Germany, 1998).
A crystal of approximate dimensions 0.166 × 0.057 × 0.051
mm3 was selected and mounted on a glass fiber. A total of
24 037 reflections (-14 e h e 14, -19 e k e 17, -26 e l e
27) were collected at T ) 293(2) K in the θ range from 1.77 to
25.50°, of which 8379 were unique (Rint ) 0.1273); Mo KR
radiation (λ ) 0.71073 Å). The residual peak and hole electron
density were 1.134 and -1.579 e/Å3. The absorption coefficient
was 3.573 mm-1. The least-squares refinement converged
normally with residuals of R1 ) 0.1342 (all data), wR2
)
0.1273, and GOF ) 0.976 [I > 2σ(I)]. C50H38Cl6P2Pt, orthor-
hombic, space group P212121, a ) 12.2983(7) Å, b ) 15.9577-
(9) Å, c ) 23.0064(14) Å, R ) 90°, â ) 90°, γ ) 90°, V )
4510.7(5) Å3, Z ) 4, Fcalcd ) 1.632 g/cm3, F(000) ) 2192, R(F)
) 0.0819, wR(F2) ) 0.1105.
Cr ysta llogr a p h ic Deta ils for 16. Colorless blocklike
crystals were grown from a solution of 16 in CHCl3. A crystal
of approximate dimensions 0.53 × 0.48 × 0.32 mm3 was
selected and mounted on
a glass fiber. A total of 6080
reflections (-14 e h e 13, -8 e k e 6, -14 e l e 16) were
collected at T ) 293(2) K in the θ range from 1.87 to 22.49°, of
which 1917 were unique (Rint ) 0.0192); Mo KR radiation (λ
) 0.71073 Å). The residual peak and hole electron density were
1.279 and -0.185 e/Å3. The absorption coefficient was 0.076
mm-1. The least-squares refinement converged normally with
residuals of R1 ) 0.0666 (all data), wR2 ) 0.1795, and GOF )
1.110 [I > 2σ(I)]. C18H16O2, monoclinic, space group P21/c, a )
13.104(3) Å, b ) 7.811(1) Å, c ) 14.904(3) Å, R ) 90°, â )
103.259(3)°, γ ) 90°, V ) 1485.0(5) Å3, Z ) 4, Fcalcd ) 1.182
g/cm3, F(000) ) 560, R(F) ) 0.0596, wR(F2) ) 0.1713.
Cr ysta llogr a p h ic Deta ils for th e Molecu la r Aggr ega te
of (()-2 a n d 4,4′-Bip yr id in e. Colorless irregular-shaped
crystals were grown from a solution of (()-2 (1 molar equiv)
and 4,4′-bipyridine (2 molar equiv) in CH3Cl. A crystal of
approximate dimensions 0.403 × 0.116 × 0.105 mm3 was
selected and mounted on
a glass fiber. A total of 7621
reflections (-13 e h e 8, -20 e k e 17, -22 e l e 22) were
collected at T ) 293(2) K in the θ range from 2.44 to 28.39°, of
which 4306 were unique (Rint ) 0.0751); Mo KR radiation (λ
) 0.71073 Å). The residual peak and hole electron density were
0.152 and -0.140 e/Å3. The absorption coefficient was 0.081
mm-1. The least-squares refinement converged normally with
residuals of R1 ) 0.1175 (all data), wR2 ) 0.1094, and GOF )
0.892 [I > 2σ(I)]. C34H24N2O2, monoclinic, space group Cc, a )
9.9763(3) Å, b ) 15.076(3) Å, c ) 17.382(5) Å, R ) 90°, â )
106.227(8)°, γ ) 90°, V ) 2510.1(12) Å3, Z ) 4, Fcalcd ) 1.303
g/cm3, F(000) ) 1032, R(F) ) 0.0591, wR(F2) ) 0.0903.
Cr ysta llogr a p h ic Deta ils for th e Molecu la r Aggr ega te
of (S)-2 a n d 4,4′-Bip yr id in e. Colorless irregular-shaped
crystals were grown from a solution of (S)-2 (1 molar equiv)
and 4,4′-bipyridine (2 molar equiv) in CH2Cl2. A crystal of
approximate dimensions 0.876 × 0.790 × 0.713 mm3 was
selected and mounted on a glass fiber. A total of 21 534
reflections (-11 e h e 14, -10 e k e 14, -38 e l e 38) were
collected at T ) 293(2) K in the θ range from 1.99 to 28.36°, of
which 4224 were unique (Rint ) 0.1029); Mo KR radiation (λ
) 0.71073 Å). The residual peak and hole electron density were
0.189 and -0.192 e/Å3. The absorption coefficient was 0.077
mm-1. The least-squares refinement converged normally with
residuals of R1 ) 0.0661 (all data), wR2 ) 0.1047, and GOF )
0.903 [I > 2σ(I)]. C44H32N4O2, monoclinic, space group Cc,
P43212, a ) 10.8989(6) Å, b ) 10.8989(6) Å, c ) 29.337(2) Å, R
) 90°, â ) 90°, γ ) 90°, V ) 3484.8(4) Å3, Z ) 4, Fcalcd ) 1.237
g/cm3, F(000) ) 1362, R(F) ) 0.0447, wR(F2) ) 0.0985.
Cr ysta llogr a p h ic Deta ils for 18. Colorless prismatic
crystals were grown from a solution of 18 in CHCl3. A crystal
of approximate dimensions 0.20 × 0.20 × 0.30 mm3 was
selected and mounted on
a glass fiber. A total of 3277
reflections were collected at T ) 293(0) K in the 2θ range from
13.62 to 21.49°, of which 3073 were unique (Rint ) 0.0066);
Mo KR radiation (λ ) 0.71069 Å). The residual peak and hole
electron density were 0.73 and -0.87 e/Å3. The linear absorp-
tion coefficient, µ, for Mo KR radiation was 69.5 cm-1. The
least-squares refinement converged normally with residuals
of R1 ) 0.055 (all data), wR2 ) 0.067, and GOF ) 2.18 [I >
3.00σ(I)]. C18H15O2Br3, triclinic, space group P1h(2), a ) 9.420-
(4) Å, b ) 11.697(5) Å, c ) 9.226(3) Å, R ) 106.56(3)°, â )
96.68(4)°, γ ) 112.08(3)°, V ) 874.0(7) Å3, Z ) 2, Fcalcd ) 1.911
g/cm3, F(000) ) 488.00.
Cr ysta llogr a p h ic Deta ils for 13. Colorless crystals were
grown from a solution of 13 in CHCl3. A crystal of good quality
was selected and mounted on a glass fiber. A total of 14 347
reflections (-18 e h e 18, -13 e k e 17, -13 e l e 18) were
collected at T ) 293(2) K in the θ range from 1.59 to 28.21°, of
which 5558 were unique (Rint ) 0.1682); Mo KR radiation (λ
) 0.71073 Å). The residual peak and hole electron density were
0.162 and -0.178 e/Å3. The absorption coefficient was 0.406
mm-1. The least-squares refinement converged normally with
residuals of R1 ) 0.3003 (all data), wR2 ) 0.0720, and GOF )
0.371 [I > 2σ(I)]. C27H21Cl3O2, monoclinic, space group P21/c,
a ) 14.304(2) Å, b ) 13.250(2) Å, c ) 14.068(2) Å, R ) 90°, â
) 116.378(3)°, γ ) 90°, V ) 2388.6(7) Å3, Z ) 4, Fcalcd ) 1.345
g/cm3, F(000) ) 1000, R(F) ) 0.0355, wR(F2) ) 0.0498.
Cr ysta llogr a p h ic Deta ils for 19. Colorless crystals were
grown from a solution of 19 in CH3OH. A crystal of ap-
proximate dimensions 0.35 × 0.24 × 0.17 mm3 was selected
and mounted on a glass fiber. A total of 27 018 reflections (-10
e h e 12, -22 e k e 24, -27 e l e 24) were collected at T )
293(2) K in the θ range from 1.45 to 28.18°, of which 9424
were unique (Rint ) 0.2158); Mo KR radiation (λ ) 0.71073 Å).
The residual peak and hole electron density were 0.654 and
-0.413 e/Å3. The absorption coefficient was 0.192 mm-1. The
least-squares refinement converged normally with residuals
of R1 ) 0.3396 (all data), wR2 ) 0.2849, and GOF ) 0.898 [I
> 2σ(I)]. C44H44O8S2, orthorhombic, space group P212121, a )
9.7766(11) Å, b ) 18.833(2) Å, c ) 21.033(3) Å, R ) 90°, â )
90°, γ ) 90°, V ) 3872.6(8) Å3, Z ) 4, Fcalcd ) 1.312 g/cm3,
F(000) ) 1616, R(F) ) 0.0823, wR(F2) ) 0.1862.
Ack n ow led gm en t. This work was supported by
grants from the Research Grants Council of the Hong
Kong Special Administrative Region, China (Project
CUHK 4264/00P), The Croucher Foundation (Hong
Kong), and the Area of Excellence Scheme established
under the University Grants Committee of the Hong
Kong Special Administrative Region, China (Project No.
AoE/P-10/01). J .F.W. thanks the Croucher Foundation
(Hong Kong) for a Shanghai Studentship. The authors
would like to thank Professors Xi-Yan Lu, Li-Xin Dai,
Guo-Qiang Lin, and Xue-Long Hou for helpful discus-
sion.
Su p p or tin g In for m a tion Ava ila ble: Synthesis of 2,2′-
bis(bromomethyl)-6,6′-dimethoxy biphenyl (7), complete ex-
perimental data of the X-ray crystallographic determination
of 16, 18, 13, 19, 25, 27, and molecular complexes of 4,4′-
bipyridine with (()-2 and (S)-2. This material is available free
of charge via the Internet at http://pubs.acs.org.
Cr ysta llogr a p h ic Deta ils for 27. Colorless irregular-
shaped crystals were grown from a solution of 27 in CH2Cl2.
J O0302408
J . Org. Chem, Vol. 68, No. 23, 2003 8931