Dendritic, 1,1'-binaphthalene-derived cleft-type receptors (dendroclefts) for the molecular recognition of pyranosides

Article abstract of DOI:10.1002/1522-2675(20000705)83:7<1346::AID-HLCA1346>3.0.CO;2-3

Two series of optically active, cleft-type dendritic receptors (dendroclefts) for carbohydrate recognition were prepared by attaching Frechet-type dendrons via ethynediyl linkers to a core consisting of one or two 1,1'-binaphthalene-2,2'-diyl phosphate mo

Full text of DOI:10.1002/1522-2675(20000705)83:7<1346::AID-HLCA1346>3.0.CO;2-3

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Helvetica Chimica Acta ± Vol. 83 (2000)
Dendritic, 1,1'-Binaphthalene-Derived Cleft-Type Receptors (Dendroclefts)
for the Molecular Recognition of Pyranosides
by Anja Bähr, BeÂatrice Felber, Katharina Schneider, and François Diederich*
Laboratorium für Organische Chemie, Eidgenössische Technische Hochschule, ETH-Zentrum,
Universitätstrasse 16, CH-8092 Zürich
Two series of optically active, cleft-type dendritic receptors (dendroclefts) for carbohydrate recognition
Â
were prepared by attaching Frechet-type dendrons via ethynediyl linkers to a core consisting of one or two 1,1'-
binaphthalene-2,2'-diyl phosphate moieties. Sugar substrates were expected to bind via bidentate ionic H-
bonding of two OH groups to the phosphodiester core and, additionally, to undergo van der Waals and CH ´´´ p
interactions with the aromatic rings of the surrounding dendritic wedges. The synthesis of the dendritic receptors
G-1-(S)-1, G-2-(S)-2, and G-3-(S)-3 (Fig. 1; G-x ˆ dendritic generation) with a single binaphthalene core
started from 3,3'-diethynylated MOM-protected (MOM ˆ methoxymethyl) 1,1'-binaphthalene-2,2'-diol (S)-13
Â
to which the Frechet-type dendrons of generations 1 ± 3 were attached via Sonogashira cross-coupling
(Scheme 3). MOM-Ether deprotection followed by phosphodiester formation and ion exchange provided the
targeted receptors. By a similar route, receptor G-1-(S)-23 with dendritic wedges capped with oligoether groups
was obtained (Scheme 4). In receptor G-1-(S)-26, the ethynediyl linker was omitted, and, in its synthesis, the
dendritic wedges were attached to MOM-protected 3,3'-diiodo-1,1'-binaphthalene-2,2'-diol by Suzuki cross-
coupling (Scheme 5). The synthesis of the dendritic receptors G-2-(S,S)-42 and G-1-(S,S)-43 with two
binaphthalene moieties at the core (Fig. 3) started from diethynylated (S,S)-39 and (S,S)-33, which contain two
MOM-protected 1,1'-binaphthalene-2,2'-diol moieties bridged by p-phenylene or buta-1,3-diynediyl linkers,
respectively, and was completed by attachment of the dendritic wedges by Sonogashira coupling, MOM-ether
deprotection, phosphodiester formation, and ion exchange (Schemes 9 and 10). By an alternative route, the C-
frame of receptor G-2-(S,S)-41 was prepared by coupling the dendron to dialkynylated 1,1'-binaphthalene (S)-
44, followed by oxidative Glaser-Hay coupling (Scheme 8). For control studies, the non-dendritic reference
receptors (S)-4 and (S)-5 (Fig. 1) with one and (S,S)-31 and (S,S)-32 (Fig. 2) with two 1,1'-binaphthalene-2,2'-
diyl phosphate moieties were also prepared. 1H-NMR Complexation studies with the dendritic receptors
containing one binaphthalene core and octyl glycosides 53 ± 55 in CD3CN and CDCl3 (Tables 2 ± 4) revealed that
ionic H-bonding between the phosphodiester core in the dendritic receptors and the sugar OH groups provides
the major driving force for stoichiometric 1:1 host-guest association. A smaller, yet significant contribution to
the binding free enthalpy was also provided by interactions between the sugar guests and the dendritic wedges.
Binding selectivity was weak in all cases, and only small changes in association strength were observed as a
function of dendritic generation. In studies with the dendritic receptors, which contain two binaphthalene
moieties at the core, higher-order complex stoichiometries prevented the determination of quantitative binding
data. As a result of unfavorable steric interactions between the dendritic wedges, these flexible receptor systems
apparently avoid adopting the ꢀsynꢁ-conformation with convergent phosphodiester sites that is required for
efficient 1 :1 host-guest complexation.
1. Introduction. ± Molecular recognition between two or more complementary
binding partners is extremely sensitive to the polarity of the surrounding environment.
For example, the hydrophobic (or solvatophobic) effect is almost worthless in benzene
[1] and solvent-exposed H-bonds count for little in H2O [2]. Even binding selectivity
can change with solvent environment [3][4]. It is, therefore, not surprising that the
microenvironment at biological recognition sites is carefully controlled in order to
achieve strong and selective complexation. Thus, small-molecule binding sites in

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proteins are usually buried within a polypeptide superstructure that precisely controls
the environmental micropolarity, the position of the convergent amino-acid residues
participating in the recognition process, and even the number of solvent molecules
present [5].
In the early 90s, researchers recognized the ability of dendritic branching to mimic
functions of biological polypeptide superstructures and to create specific micro-
environmental effects in the interior of dendrimers [6][7] (for surveys on dendrimer
chemistry, see [8 ± 12]). Dendritic iron porphyrins were found to be valid models of
cytochromes: the dendritic branches create a unique local microenvironment around
the isolated electroactive core, and this shielding from solvent profoundly alters the
redox potential of the FeIII/FeII couple [13]. Other investigations addressed the
modulation of binding affinity and selectivity at cyclophane [14] and cleft-type [15]
binding sites buried at the dendritic core (for general surveys on supramolecular
dendrimer chemistry, see [16]).
Efficient and selective complexation of carbohydrates by synthetic receptors in
aqueous solution remains a true frontier in supramolecular chemistry [17][18]. In
biological carbohydrate recognition [5][19], the interplay of H-bonding and apolar as
well as hydrophobic interactions is still poorly understood. It has, however, become
clear that both modes of interactions are essential for stable and selective complexation
in protic solvents. Therefore, we became interested in developing receptors featuring
an efficient ionic H-bonding site buried inside a lipophilic dendritic shell. The novel
dendritic hosts described in this paper contain a core that consists of one or two
optically active 1,1'-binaphthalene-2,2'-diyl phosphate moieties. These phosphodiester
groups had previously been found to provide highly efficient ionic H-bonding sites ±
even in protic solvent mixtures ± when introduced into macrocyclic receptors for mono-
Â
and disaccharides [20][21]. As dendritic surrounding, we chose Frechet-type wedges,
which consist of resorcinol-ether repeating units [22][23]. We hoped that the sugar
guests, which dock at the phosphodiester core, would form a large number of van der
Waals contacts with these branches and undergo efficient CH ´´´ p interactions [24]
with their aromatic rings. The latter interactions have been observed in numerous
X-ray crystal structures of protein-carbohydrate complexes [5][25] and they have
also been shown to contribute to sugar binding by artificial receptors [26]. At the
same time, we expected that the lipophilic dendritic branching would shield the
internal binding site from bulk polar solvent, thereby enhancing the strength of the
host-guest H-bonds. Here, we describe the synthesis of these novel dendritic cleft-type
receptor systems (dendroclefts [15]) and investigations of their sugar-binding ability in
1
different solvents on the basis of H-NMR binding titrations and extraction experi-
ments.
2. Results and Discussion. ± 2.1. Synthesis of Receptors with a Single 1,1'-
Binaphthalene-2,2'-diyl Phosphate Core. We first prepared receptors G-1-(S)-1,
G-2-(S)-2, and G-3-(S)-3 of first to third generation together with comparison
compounds (S)-4 and (S)-5 (Fig. 1). By their general shape ± featuring a H-bonding
site surrounded by two dendrons ± they resemble two series of dendritic hosts
previously prepared for sugar [15] and amidinium salt complexation [23], respec-
tively.

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Fig. 1. Dendritic hosts with a single 1,1'-binaphthalene-2,2'-diyl phosphate core and reference compounds
Â
For the synthesis of the Frechet-type dendrons, 4-iodoresorcinol (5-iodobenzene-
1,3-diol) [23] was prepared by Sandmeyer reaction [27] of 3,5-dimethoxyaniline to give
5-iodo-1,3-dimethoxybenzene, followed by methyl-ether cleavage. Subsequent Wil-
liamson ether synthesis with PhCH2Br, 6 [22], or 7 [22] afforded dendrons G-1-8, G-2-9,
and G-3-10, respectively (Scheme 1). We also prepared the dendritic wedge G-1-11
starting from benzyl-bromide derivative 12 [28].
The non-dendritic reference compounds were prepared starting from (S)-13 [29]
(Scheme 2) (for ethynylated 1,1'-binaphthalene-2,2'-diol derivatives, see [30]). MOM-
Ether cleavage (MOM ˆ methoxymethyl) afforded (S)-14, and the cyclic phospho-
diester (S)-4 was obtained using POCl3 and Et3N [21b], followed by ion-exchange
‡
chromatography (Dowex (Bu4N )). Sonogashira cross-coupling [31] of (S)-13 with PhI
gave (S)-15 in excellent yield (97%). MOM-Ether deprotection provided (S)-16, and
formation of the cyclic phosphodiester, followed by ion-exchange chromatography, led
to the second reference compound (S)-5.
A protocol similar to that used in the synthesis of (S)-5 was applied to the synthesis
of the dendritic target molecules. Thus, the sequence Sonogashira cross-coupling !
MOM-ether deprotection ! phosphodiester formation and ion-exchange provided the
first-generation ((S)-13 and G-1-8 ! G-1-(S)-17 ! G-1-(S)-18 ! G-1-(S)-1), second-

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Scheme 1. Syntheses of Dendritic Wedges
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a) K2CO3, acetone or acetone/MeCN 1:1, [18]crown-6, 558, 24 ± 60 h; 95% (G-1-8); 90% (G-2-9); 79% (G-3-
10). b) K2CO3, acetone, [18]crown-6, 608, 20 h; 43%.
generation ((S)-13 and G-2-9 ! G-2-(S)-19 ! G-2-(S)-20 ! G-2-(S)-2), and third-
generation dendroclefts ((S)-13 and G-3-10 ! G-32-(S)-21 ! G-3-(S)-22 ! G-3-(S)-
3) (Scheme 3).
Scheme 2. Synthesis of Non-dendritic Reference Compounds
a) Conc. HCl (cat.), THF/MeOH, 208, 4 ± 12 h; 99% ((S)-14); 75% ((S)-16). b) POCl3, Et3N, CH2Cl2, 208, 3 ±
‡
6 h; then THF/H2O, 30-408, 12 h, then Dowex (Bu4N ), CH2Cl2/MeCN 1:1; 38% ((S)-4); 54% ((S)-5). c) PhI,
[PdCl2(PPh3)2], CuI, THF/(i-Pr)2NH, 408; 2 h, 97%.

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Scheme 3. Synthesis of the Dendritic Receptors with One Phosphodiester Core
a) [PdCl2(PPh3)2], CuI, THF/(i-Pr)2NH, 408, 12 h, 85% ((S)-17); 71% ((S)-19). b) Conc. HCl (cat.), THF/
MeOH, 208, 12 h; 79% ((S)-18); 85% ((S)-22). c) POCl3, Et3N, CH2Cl2, 208, 3 h; then THF/H2O, 408, 12 h; then
‡
Dowex (Bu4N ), CH2Cl2/MeCN 1:1; 71% (G-1-(S)-1); 54% (G-2-(S)-2 from (S)-19); 52% (G-1-(S)-3). d)
[PdCl2(dppf)], CuI, THF/(i-Pr)2NH, 408, 2 h; 57% (dppf ˆ 1,1'-bis(diphenylphosphanyl)ferrocene). For G-1 to
G-3, see Fig. 1.
We examined different cross-coupling conditions and observed the best yield when
(S)-13 was added slowly over a period of 30 min to a suspension of catalyst and
iodoaryl dendron. Both catalysts, [PdCl2(PPh3)2] and [PdCl2(dppf)], gave good results
for the coupling of the first- and second-generation dendrons. With the third-generation
derivative G-3-10, we observed a superior performance for [PdCl2(dppf)] over
[PdCl2(PPh3)2]. The coupling yields decreased from 85% (for G-1-8) to 57% (for G-3-
10) due to the increased steric hindrance of the dendron. In all cases, the formation of
homo-coupled products occurred as major side reaction, but purification could be
easily achieved by GPC (gel-permeation chromatography).
For MOM-ether deprotection, it was necessary to use very mild acidic conditions to
avoid 5-endo-dig cyclization [32] of the free OH groups with the adjacent ethynyl
moieties [29]. Following formation of the phosphodiester and prior to the ion-exchange
chromatography, purification by column chromatography (SiO2; CH2Cl2 containing 1 ±
3% Et3N) was required to obtain analytically pure target receptors.
Receptor G-1-(S)-23 with polyether capping groups was prepared by an analogous
sequence ((S)-13 and G-1-11 ! G-1-(S)-24 ! G-1-(S)-25 ! G-2-(S)-23) (Scheme 4).
To investigate the influence of different distances between the first aromatic rings of
the dendritic branches and the core phosphodiester group ± the docking point for the
sugar guest ± receptor G-1-(S)-26, which lacks the acetylenic linker between
binaphthalene and dendritic wedges, was prepared (Scheme 5). The synthesis started
from diiodinated (S)-27 [29], which was cross-coupled under Suzuki conditions [33] to
the boronate dendron 28. This reaction was best conducted in 1,2-dimethoxyethane

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Scheme 4. Synthesis of the Dendritic Receptor G-1-(S)-23
a) [PdCl2(dppf)], CuI, THF/(i-Pr)2NH, 408, 12 h; 65%. b) Conc. HCl (cat.), THF/MeOH, 208, 12 h. c) POCl3,
‡
Et3N, CH2Cl2, 208, 3 h; then THF/H2O, 408, 12 h; then Dowex (Bu4N ), CH2Cl2/MeCN 1:1; 61% (from G-1-
(S)-24).
Scheme 5. Synthesis of Dendritic Receptor G-1-(S)-26
a) [PdCl2(dppf)], DME, aq. Na2CO3 soln., 858, 3 h; 80%. b) Conc. HCl (cat.), THF/MeOH, 208, 20 h. c) POCl3,
‡
Et3N, CH2Cl2, 208, 4 h; then THF/H2O, 408, 12 h; then Dowex (Bu4N ), CH2Cl2/MeCN 1:1; 93% (from G-1-
(S)-29).
(DME) with [PdCl2(dppf)] as the catalyst and aq. Na2CO3 solution as the base,
providing G-1-(S)-29 in 80% yield.
Boronate 28 was prepared by cross-coupling of (pinacolato)boron with G-1-8 in
dioxane with [PdCl2(dppf)] and Et3N [34]. In the Pd-catalyzed cross-coupling of

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(pinacolato)boron (or bis(pinacolato)diboron) with either an iodo- or bromoaryl
substrate to give the corresponding boronate, reduction is frequently observed as a
major side reaction [34]. According to the 1H-NMR spectra of the crude product, the
desired compound 28 was formed as the major product (ca. 65%) together with the
reduction product 1,3-bis(benzyloxy)benzene (ca. 35%). Decomposition of 28 during
column chromatography (SiO2) could be suppressed by adding Et3N (0.5%) to the
eluent (hexane/AcOEt 10 :1), and pure 28 was then obtained in 54% yield. When
the same reaction was performed with the dendritic wedge G-2-9, the desired product
was formed in ca. 50% yield (1H-NMR spectrum of the crude product), but
here decomposition could not be avoided during the subsequent column chromatog-
raphy.
The inverse approach towards G-1-(S)-29, namely coupling of the iodoaryl dendron
G-1-8 with a 1,1'-binaphthalenediboronic acid or ester, was less successful. When we
attempted to transform 3,3'-diiodinated 1,1'-binaphthalene (S)-27 into the bis(boronic
acid) or the corresponding diester by lithiation and quenching with trimethoxyborane
[35][36], complex product mixtures were isolated. The same result was obtained by the
above-described Pd-catalyzed cross-coupling reaction with (pinacolato)boron or
bis(pinacolato)diboron. The synthesis of G-1-(S)-26 was finally completed via the
sequence G-1-(S)-29 ! G-1-(S)-30 ! G-1-(S)-26 (Scheme 5).
2.2. Synthesis of Receptors with a Bis(1,1'-binaphthalene-2,2'-diyl Phosphate) Core.
We first prepared the two non-dendritic reference compounds (S,S)-31 and (S,S)-32
(Fig. 2). For the synthesis of the former, buta-1,3-diynediyl-bridged (‡)-(S,S)-33 was
obtained by the route described in [29] for its antipode (À)-(R,R)-33 (Scheme 6).
MOM-Ether deprotection (!(S,S)-34) and phosphodiester formation, followed by
ion-exchange, afforded (S,S)-31.
The synthesis of the reference compound (S,S)-32 with a p-phenylene-spacer
started with the unsymmetrically functionalized 1,1'-binaphthalene derivatives (S)-35
or (S)-36, which were prepared from symmetrical diiodinated (S)-27 by single
Sonogashira cross-coupling under carefully controlled conditions (Scheme 7). When
2.0 equiv. of R3SiÀCꢀCH (R ˆ Me or i-Pr) in very dilute solution at 408 were used, and
the reaction was immediately quenched after the appearance of dialkynylated product
Fig. 2. Non-dendritic reference compounds (S,S)-31 and (S,S)-32

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Scheme 6. Synthesis of the Buta-1,3-diyne-1,4-diyl-Linked Reference Compound (S,S)-31
a) Conc. HCl (cat.), THF/MeOH, 208, 10 h. b) POCl3, Et3N, CH2Cl2, 208, 3 h; then THF/H2O, 308, 12 h; then
‡
Dowex (Bu4N ), CH2Cl2/MeCN 1:1; 52% (from (S,S)-33).
(generally after 3 ± 5 h; TLC), (S)-35 and (S)-36, respectively, were obtained in 30%
yield. Other conditions (such as ambient temperature, 0.5 ± 1.0 equiv. of R3SiÀCꢀCH)
gave worse results, with chromatographic product separation becoming very tedious
Scheme 7. Synthesis of the p-Phenylene-Linked Reference Compound (S,S)-32
a) R3SiÀCꢀCH, [PdCl2(PPh3)2], CuI, Et3N, toluene, 408, 3 ± 4 h; 30%. b) [PdCl2(dppf)], aq. Na2CO3 soln.,
benzene, EtOH, 808, 12 h; 74% (from (S)-36). c) Bu4NF, THF, 208, 1 h; 97%. d) Conc. HCl (cat.), THF/MeOH,
‡
208, 10 h. e) POCl3, Et3N, CH2Cl2, 208, 3 h; then THF/H2O, 308, 12 h; then Dowex (Bu4N ), CH2Cl2/MeCN 1:1;
55% (from (S)-39).

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and difficult. Due to greater differences in polarity, the (i-Pr)3Si-protected derivative
(S)-36 was more readily separated from dialkynylated side product than the Me3Si-
protected analog.
For the subsequent Suzuki cross-coupling to build the C-skeleton of (S,S)-32,
bis[boronate] 37 was prepared by Pd-catalyzed cross-coupling [34], starting from
(pinacolato)boron and 1,4-diiodobenzene. The second coupling occurred only after
heating the mixture for 12 h to 808. In this conversion, the monosubstituted reduction
product, 2-phenyl-4,4,5,5-tetramethyl-1,3,2-dioxoborolane, was also formed in signifi-
cant yields (up to 50%). Partial decomposition occurred during column chromatog-
raphy, but purification could be achieved by recrystallization from hexane to provide
pure 37 as white needles in 44% yield. Compound 37 is an interesting new building
block that can be applied to diverse molecular scaffolding.
The Suzuki cross-coupling required strongly basic conditions and protic solvent
mixtures and could, therefore, not be conducted with (S)-35. The Me3Si alkyne
protecting group is too labile under these conditions, and cleavage, followed by
undesirable homo-coupling, became the predominant reaction channel.
The cross-coupling between (i-Pr)3Si-protected (S)-36 and 37 under formation of
(S,S)-38 was examined under various conditions. It was found that the reaction was best
conducted with [PdCl2(dppf)] as catalyst in a mixture of benzene, EtOH, and aq.
Na2CO3 solution. After 3 h at 808, the product had been already formed in good yields.
Repeated addition of catalyst over 12 h finally afforded (S,S)-38 after GPC in 74%
yield (Scheme 7). Removal of the (i-Pr)3Si groups with Bu4NF proceeded smoothly and
gave (S,S)-39 in 75% yield. MOM Deprotection (!(S,S)-40) and phosphodiester
formation, followed by ion-exchange, completed the synthesis of (S,S)-32.
The three dendroclefts G-2-(S,S)-41, G-2-(S,S)-42, and G-1-(S,S)-43 with bis(1,1'-
binaphthalene-2,2'-diyl phosphate) cores (Fig. 3) were prepared as described below.
Fig. 3. Dendritic receptors with bis(1,1'-binaphthalene-2,2'-diyl phosphate) cores

Helvetica Chimica Acta ± Vol. 83 (2000)
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For the synthesis of G-2-(S,S)-41, mono-deprotected bis-alkynylated (S)-44 [29]
was subjected to the Sonogashira cross-coupling with G-2-9 to give G-2-(S)-45
(Scheme 8). The best yield (67%) was obtained when the alkyne was added slowly to
the mixture of iodinated dendron, catalysts, and base; under these conditions homo-
coupling of the alkyne was largely avoided. Purification of G-2-(S)-45 was best
accomplished by GPC. Alkyne deprotection provided G-2-(S)-46, which was subjected
to Glaser-Hay homo-coupling to give G-2-(S,S)-47 in 81% yield after GPC. Finally, the
standard sequence of MOM-ether deprotection ( ! G-2-(S,S)-48) and phosphodiester
formation, followed by ion-exchange, led to dendrocleft G-2-(S,S)-41 in a high overall
yield of 13% starting from (S)-1,1'-binaphthalene-2,2'-diol [29].
The synthesis of dendritic receptor G-2-(S,S)-42 with a p-phenylene linker between
the two 1,1'-binaphthalene moieties started from (S,S)-39 that was cross-coupled with
iododendron G-2-9 to give G-2-(S,S)-49 (Scheme 9). MOM-Ether deprotection (!G-
2-(S,S)-50), phosphodiester formation, and ion-exchange afforded the desired target
compound.
A similar sequence led from diethynylated (S,S)-33 to the third dendrocleft G-1-
(S,S)-43 with a bis[1,1'-binaphthalene] core and polyether capping groups (Scheme 10).
Sonogashira cross-coupling with iodo dendron 14 ( ! G-1-(S,S)-51), MOM-ether
deprotection ( ! G-1-(S,S)-52), and phosphodiester formation, followed by ion-
exchange, afforded the desired target compound. Due to the high polarity of G-1-(S,S)-
43, with its polyether branching, chromatography (SiO2) required a very polar solvent
mixture (CH2Cl2/Et3N 95 :5). Under these conditions, however, some SiO2 was
Scheme 8. Synthesis of the Dendritic Bis(1,1'-binaphthalene-2,2'-diyl Phosphate) Receptor G-2-(S)-41
a) [PdCl2(PPh3)2], CuI, THF/(i-Pr)2NH, 458, 5 h; 69%. b) K2CO3, THF, MeOH, 208, 2 h. c) CuCl, TMEDA
(N,N,N',N'-tetramethylethylenediamine), air, CH2Cl2, 208, 1.5 h; 81%. d) Conc. HCl (cat.), THF/MeOH, 208,
‡
10 h. e) POCl3, Et3N, CH2Cl2, 208, 3 h; then THF/H2O, 308, 12 h; then Dowex (Bu4N ), CH2Cl2/MeCN 1:1;
82% (from G-2-(S,S,)-47).

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Scheme 9. Synthesis of the Dendritic Bis(1,1'-binaphthalene-2,2'-diyl Phosphate) Receptor G-2-(S)-42
a) [PdCl2(dppf)], CuI, THF/(i-Pr)2NH, 408, 4 h; 48%. b) Conc. HCl (cat.), THF/MeOH, 208, 10 h. c) POCl3,
‡
Et3N, CH2Cl2, 208, 3 h; then THF/H2O, 308, 12 h; then Dowex (Bu4N ), CH2Cl2/MeCN 1:1; 79% (from G-2-
(S,S)-48).
Scheme 10. Synthesis of the Dendritic Bis(1,1'-binaphthalene-2,2'-diyl Phosphate) Receptor G-1-(S)-43
a) [PdCl2(PPh3)2], CuI, THF/(i-Pr)2NH, 408, 4 h; 34%. b) Conc. HCl (cat.), THF/MeOH, 208, 12 h. c) POCl3,
‡
Et3N, CH2Cl2, 208, 4.5 h; then THF/H2O, 408, 12 h; then Dowex (Bu4N ), CH2Cl2/MeCN 1 :1; 35% (from G-1-
(S,S)-51).
dissolved, which necessitated subsequent extractions with CH2Cl2/H2O and led to a low
yield (35%) in the last step of the synthesis.
2.3. Sugar Complexation with the Dendritic Receptors. Binding studies with the octyl
1
glucosides 53 ± 55 were performed by 500-MHz H-NMR titrations at 300 K. In most
cases, the complexation-induced downfield shifts of the proton signals of the receptor,

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held at constant concentration, were monitored as a function of guest concentration.
Some inverse titrations (constant guest concentration and variable receptor concen-
tration), following the upfield shifts of signals of the monosaccharides, were also
undertaken for comparison. The standard solvent for the titrations was CD3CN,
although some studies were also executed in less polar (CDCl3, favoring host-guest H-
bonding) or more polar solvent systems (CD3CN/MeOD (98 :2), (CD3)2SO, and even
D2O, which favor apolar interactions and hydrophobic desolvation) [1]. In several
titrations, the evaluation of the thermodynamic quantities Ka [mÀ1] and DG0
[kcal molÀ1] for 1:1 host-guest complexation was hampered by the formation of
complexes with higher stoichiometry.
1
2.3.1. H-NMR Binding Studies with Receptors Featuring One 1,1'-Binaphthalene-
2,2-diyl-Phosphate Recognition Site. By comparing the sugar-binding ability of
dendroclefts G-1-(S)-1, G-2-(S)-2, and G-3-(S)-3 to that of reference compounds
(S)-4 and (S)-5, which lack the dendritic shell, we hoped to identify the contributions to
Â
the binding free enthalpy resulting from the Frechet-type dendrons in the former. The
dendritic shell could provide an environment of reduced polarity around the
phosphodiester site, thereby strengthening the bidentate ionic H-bonding to two OH
groups of the sugar substrate. Furthermore, the apolar regions of the sugar substrates
could interact favorably with the aromatic rings in the dendritic wedges. Therefore, we
expected increasing host-guest binding strength with enhanced dendritic coverage.
2.3.1.1. Studies with the Reference Receptors. For the small cleft-type receptors (S)-4
and (S)-5, it could not be excluded that two such molecules would bind to one sugar
molecule, thereby forming complexes with 2 :1 host-guest stoichiometry. The analysis
of the 1H-NMR data (300 K), by Jobꢁs method of continuous variation [39], however,
clearly confirmed the exclusive formation of a complex with 1:1 host-guest
stoichiometry between (S)-5 and 55 in CD3CN. In this experiment at a total
concentration of the binding partners of 2.0 mm, the complexation-induced upfield
shift Dd of the sugar resonance HÀC(1) was monitored as a function of the mole
fraction of the sugar xsugar. The plot of Dd/xsugar as a function of xsugar gave a clear
maximum at 0.5, indicating a 1:1 host-guest stoichiometry.
The same experiment with (S)-4 and 55 in CD3CN led to insignificant changes in
both Dd/xsugar and Dd/xreceptor, which prevented an accurate determination of the
complex stoichiometry. In CDCl3, the Job plot for this association gave a flat curve
without a clear maximum, thereby preventing any precise analysis, too.
1
In H-NMR binding titrations with (S)-5, the receptor exhibited small (Ddsat
<
0.1 ppm) but highly reproducible complexation-induced downfield shifts of the sharp
resonances for the binaphthalene proton HÀC(4) and the phenyl proton HÀC(9) (for
the arbitrary numbering, see Fig. 1). In studies with (S)-4, the small downfield shifts

1358
Helvetica Chimica Acta ± Vol. 83 (2000)
(Ddsat < 0.1 ppm) of the binaphthalene resonance HÀC(4) and the ethynyl signal were
followed. Table 1 gives the averaged association constants Ka [mÀ1] and complexation
free enthalphies DG0 [kcal molÀ1] calculated by nonlinear least-square curve-fitting
analysis of the titration data with the program Associate V.1.6 [40].
Reference receptor (S)-4 binds octyl glucosides 53 ± 55 in CD3CN with low affinity
(Ka ˆ 70 ± 150 mÀ1, DG0 ˆ À2.5 to À2.9 kcal molÀ1). With the Ph-substituted receptor
(S)-5, the association constants increase (Ka ˆ 160 ± 200 mÀ1, DG0 ˆ À3.0 to
À3.1 kcal molÀ1), presumably as a result of favorable interactions (dispersion and
CH ´´´ p) between the two Ph rings and apolar regions of the sugar. An inverse titration
of (S)-5 and 55 gave a slightly higher association constant (Ka ˆ 300 mÀ1, DG0 ˆ
À3.4 kcal molÀ1). The strength of H-bonding interactions is extremely sensitive to
the environment [3], and such a discrepancy between thermodynamic data obtained
from standard and inverse titrations may well originate from the differences in the
experimental conditions. Also, the data are not corrected for possible self-association
between the binding partners that can interfere differentially in both titration modes.
As expected, a significant enhancement in the value of the association constant
(Ka ˆ 1220 mÀ1, DG0 ˆ À4.2 kcal molÀ1 for the complex of (S)-5 with 55) was obtained
when the studies were carried out in the less competitive solvent CDCl3.
All titration data discussed so far were in good agreement with a 1:1 host-guest
complexation mode. However, the binding curve that resulted from the titration of (S)-4
Table 1. Association Constants Ka [mÀ1] and Complexation Free Enthalpies DG0 [kcal molÀ1] from 1H-NMR
Binding Titrations (500 MHz) for 1 : 1 Complexes of Receptors (S)-4 and (S)-5 with Monosaccharides 53 ± 55 in
CD3CN or CDCl3 (300 K). Also shown are the calculated and, in parentheses, the maximum observed
complexation-induced shifts ([ppm], ‡ˆ downfield), Ddsat and Ddmaxobs, of the receptor signals monitored
during the titration.
b
Sugar/Solvent a)
Receptor
Ka ) [mÀ1
]
DG0 [kcal molÀ1
À 2.5
]
Ddsat (Ddmax obs) [ppm]
53/CD3CN
(S)-4
70
HÀC(4): ‡ 0.047 (‡ 0.026)
ꢀCÀH: ‡ 0.100 (‡ 0.056)
HÀC(4): ‡ 0.032 (‡ 0.020)
ꢀCÀH: ‡ 0.087 (‡ 0.044)
HÀC(4): ‡ 0.035 (‡ 0.024)
ꢀCÀH: ‡ 0.082 (‡ 0.043)
HÀC(4): ‡ 0.046 (‡ 0.042)
ꢀCÀH: ‡ 0.38 (‡ 0.27)
54/CD3CN
55/CD3CN
(S)-4
120
150
À 2.8
À 2.9
(S)-4
55/CDCl3
(S)-4 c)
960
260
2060
160
À 4.1
À 3.2
À 4.5
À 3.0
d
55/CDCl3
)
(S)-4
(S)-5
HÀC(1): À 0.049 (À 0.045) e)
HÀC(4): ‡ 0.038 (‡ 0.025)
HÀC(9): ‡ 0.080 (‡ 0.051)
HÀC(4): ‡ 0.042 (‡ 0.028)
HÀC(9): ‡ 0.074 (‡ 0.053)
HÀC(4): ‡ 0.034 (‡ 0.023)
HÀC(9): ‡ 0.078 (‡ 0.054)
HÀC(1): À 0.088 (À 0.055) e)
HÀC(4): ‡ 0.053 (‡ 0.048)
HÀC(9): ‡ 0.064 (‡ 0.058)
53/CD3CN
54/CD3CN
55/CD3CN
(S)-5
(S)-5
200
180
À 3.1
À 3.1
55/CD3CN d)
55/CDCl3
(S)-5
(S)-5
300
1220
À 3.4
À 4.2
a) Host concentration was constant at 1.0 mm, guest concentration varied between 0.3 and 12.5 mm. b) Un-
certainty in Ka estimated at 10%. c) Strongly different results for the two signals HÀC(4) and HÀC(10)
indicate higher-order stoichiometries. d) Inverse titration with constant sugar concentration (0.5 mm) and host
concentration varied between 0.2 and 6.3 mm. e) Ddsat (Ddmaxobs) of the sugar resonance HÀC(1).

Helvetica Chimica Acta ± Vol. 83 (2000)
1359
with 55 in CDCl3 exhibited only a poor fit to the 1:1 stoichiometry model. Furthermore,
the thermodynamic quantities calculated from the downfield shifts of the binaphtha-
lene resonance HÀC(4) and the ethynyl resonance differed strongly, and an inverse
titration gave a significantly higher association constant (see Table 1). These
observations can be rationalized by the formation of complexes with higher
stoichiometries, which was not further investigated in the course of this work. These
findings are in agreement with results from Job-plot analyses (see above), which had
remained inconclusive with respect to the host-guest stoichiometry.
2.3.1.2. Studies with the Dendroclefts. Compounds G-1-(S)-1, G-2-(S)-2, and G-3-
(S)-3 do not aggregate appreciably in CD3CN at concentrations below 5.0 mm, as was
1
confirmed by H-NMR dilution experiments. In binding titrations with G-1-(S)-1 and
G-2-(S)-2, the receptors exhibited small but highly reproducible downfield shifts
(Ddsat < 0.1 ppm) of the sharp binaphthalene signal (HÀC(4)) and the phenyl
resonance (HÀC(9)) (for numbering, see Fig. 1) upon addition of the monosaccharide
guests 53 ± 55. In titrations with G-3-(S)-3, the shifts of the HÀC(4) signal were
negligible and could not be evaluated. All data could be nicely fitted to the 1:1 host-
guest binding model (Table 2). This stoichiometry was confirmed by Job-plot analysis
for the complex formed between G-1-(S)-1 and 55.
The complexes formed by the first-generation dendrocleft G-1-(S)-1 were
significantly more stable (Ka ˆ 260 ± 350 mÀ1) than those of reference compound (S)-
4 (Ka ˆ 70 ± 150 mÀ1). A further, slight enhancement in binding strength was observed
with the second-generation receptor G-2-(S)-2, whereas host-guest affinity started
decreasing at the third-generation level. It can be assumed that steric hindrance by
Table 2. Association Constants Ka [mÀ1] and Complexation Free Enthalpies DG0 [kcal molÀ1] from 1H-NMR
Binding Titrations (500 MHz) for 1 : 1 Complexes of Receptors G-1-(S)-1, G-2-(S)-2, and G-3-(S)-3 with
Monosaccharides 53 ± 55 in CD3CN or CDCl3 (300 K). Also shown are the calculated and, in parentheses, the
maximum observed complexation-induced shifts ([ppm], ‡ˆ downfield), Ddsat and Ddmaxobs, of the receptor
signal HÀC(9) monitored during the titration.
Sugar/Solventa)
Receptor
Ka b) [mÀ1
]
DG0 [kcal molÀ1
]
Ddsat (Ddmaxobs) [ppm]
53/CD3CN
54/CD3CN
55/CD3CN
55/CDCl3
53/CD3CN
54/CD3CN
55/CD3CN
55/CDCl3
55/CD3CNc)
53/CD3CN
54/CD3CN
55/CD3CN
55/CDCl3
G-1-(S)-1
G-1-(S)-1
G-1-(S)-1
G-1-(S)-1
G-2-(S)-2
G-2-(S)-2
G-2-(S)-2
G-2-(S)-2
G-2-(S)-2
G-3-(S)-3
G-3-(S)-3
G-3-(S)-3
G-3-(S)-3
260
240
350
1160
270
330
370
2280
740
180
220
290
760
À 3.3
À 3.2
À 3.5
À 4.2
À 3.3
À 3.4
À 3.5
À 4.6
À 3.9
À 3.1
À 3.2
À 3.4
À 3.9
‡ 0.074 (0.055)
‡ 0.068 (‡ 0.051)
‡ 0.063 (‡ 0.050)
‡ 0.058 (‡ 0.053)
‡ 0.067 (‡ 0.055)
‡ 0.064 (‡ 0.050)
‡ 0.059 (‡ 0.047)
‡ 0.065 (‡ 0.060)
À 0.125 (À 0.084)d)
‡ 0.052 (‡ 0.034)
‡ 0.055 (‡ 0.039)
‡ 0.052 (‡ 0.040)
‡ 0.066 (‡ 0.058)
a) Host concentration was constant at 1.0 mm (0.5 mm for G-3-(S)-3, guest concentration varied between 0.3 and
12.5 mm. b) Uncertainty in Ka estimated at 10%. Similar Ka values were obtained when the complexation-
induced shift of the binaphthalene resonance (HÀC(10)) could be evaluated. c) Inverse titration with constant
sugar concentration (0.5 mm) and host concentration varied between 0.1 and 3.1 mm. d) Ddsat (Ddmaxobs
determined for the upfield shift of the sugar resonance HÀC(1).
)

1360
Helvetica Chimica Acta ± Vol. 83 (2000)
the bulky dendritic wedges starts interfering with the docking of the sugar at the
buried phosphodiester H-bonding site inside G-3-(S)-3. Substrate selectivity is low
in all cases, with a slight preference being observed for the complexation of octyl
b-d-glucoside 55. From an inverse titration (at constant sugar concentration) of G-2-
(S)-2 with 55, a higher binding constant (Ka ˆ 740 mÀ1, DG0 ˆ À3.9 kcal molÀ1) with
respect to that obtained in the standard titration (at constant receptor concentration;
Ka ˆ 370 mÀ1, DG0 ˆ À3.5 kcal molÀ1) was calculated. The same phenomenon had
already been observed in the inverse titration of reference receptor (S)-4 with 55 and
confirms the sensitivity of H-bonding interactions towards different experimental
conditions.
In titrations in CD3CN/CD3OD 98 :2, the maximum observed changes in chemical
shift of the receptor protons decreased as did the values of the association constants (Ka
in all cases ca. 100 mÀ1) calculated for the formed 1:1 complexes. This decrease in host-
guest affinity was independent of dendritic generation. Attempted titrations between
G-2-(S)-2 and 55 in (CD3)2SO ± a solvent which competes effectively for the H-bonding
donor sites in the sugar substrate ± could not be evaluated, since complexation strength
was too low. In the noncompetitive solvent CDCl3, however, binding strength was
enhanced significantly, with the second-generation receptor forming the most stable
complex with guest 55 (Ka ˆ 2280 mÀ1, À DG0 ˆ 4.6 kcal molÀ1). These solvent-depend-
ent studies clearly show that bidentate ionic H-bonding is by far the most important
interaction in the complexes formed by the dendroclefts, and that dispersion
interactions and solvophobic effects make much smaller contributions to the measured
binding free enthalpies.
When the acetylenic spacer between the 1,1'-binaphthalene core and the dendritic
shell was removed, an interesting solvent dependency of the association strength was
observed. A comparison of the complexation of the octyl glycosides by the first-
generation dendroclefts G-1-(S)-1 (Table 2) and G-1-(S)-26 (Table 3) in CD3CN
reveals a significant decrease in association strength upon removal of the ethynediyl
spacers. Thus, the complex of 55 with G-1-(S)-26 is 0.7 kcal molÀ1 less stable than the
complex formed by G-1-(S)-1. On the other hand, the association strength remains
identical (DG0 ˆ À4.2 kcal molÀ1) in CDCl3. The origin of this substantial solvent effect
Table 3. Association Constants Ka [mÀ1] and Complexation Free Enthalpies DG0 [kcal molÀ1] from 1H-NMR
Binding Titrations (500 MHz) for 1 : 1 Complexes of Receptor G-1-(S)-26 with Monosaccharides 53 ± 55 in
CD3CN and CDCl3 (300 K). Also shown are the calculated and, in parentheses, the maximum observed
complexation-induced shifts ([ppm], ‡ˆ downfield), Ddsat and Ddmaxobs, of the receptor signals HÀC(8) and
HÀC(9) monitored during the titration (for the numbering, see Scheme 5).
b
Sugar/Solventa)
Ka
)
]
DG0
[kcal molÀ1
Ddsat (Ddmaxobs) HÀC(8)
Ddsat(Ddmaxobs) HÀC(9)
[mÀ1
]
[ppm]
[ppm]
53/CD3CN
54/CD3CN
55/CD3CN
55/CD3CNc)
55/CDCl3
90
80
110
40
À 2.7
À 2.6
À 2.8
À 2.2
À 4.2
À 0.069 (À 0.035)
À 0.072 (À 0.035)
À 0.075 (À 0.043)
À 0.113 (À 0.040)
À 0.056 (À 0.053)
‡ 0.178 (‡ 0.093)
‡ 0.207 (‡ 0.104)
‡ 0.203 (‡ 0.119)
no significant shift
‡ 0.167 (‡ 0.155)
1230
b
a) Host concentration was constant at 1.0 mm, guest concentration varied between 0.3 and 12.5 mm.
Uncertainties in Ka estimated at Æ10%. ) Addition of 2% MeOD.
)
c

Helvetica Chimica Acta ± Vol. 83 (2000)
1361
remains unclear at present. It could result both from differences in the solvation of the
H-bonding groups of the binding partners and solvent-dependent interactions between
the sugar and the dendritic Ph groups of the two receptors.
The effect of solvent on association strength again changes when receptor G-1-(S)-
23 with ethynediyl spacers and oligoether capping groups is used. In CDCl3, the intro-
duction of the oligoether groups does not affect the measured binding free enthalpy,
and monosaccharide 55 forms complexes of nearly identical stability with the first-
generation receptors G-1-(S)-1 (Table 2) and G-1-(S)-23 (Table 4). In CD3CN, however,
the oligoether receptor is more effective by 0.2 ± 0.3 kcal molÀ1. Dendritic oligoether
wedges have previously been shown to participate in carbohydrate recognition,
presumably through O ´´´ HÀO H-bonding [15b]. In this present case, such interactions
seem to make a larger contribution to the binding in CD3CN than in CDCl3.
Table 4. Association Constants Ka [mÀ1] and Complexation Free Enthalpies DG0 [kcal molÀ1] from 1H-NMR
Binding Titrations (500 MHz) for 1 : 1 Complexes of Receptor G-1-(S)-23 with Monosaccharides 53 ± 55 in
CD3CN and CDCl3 (300 K). Also shown are the calculated and, in parentheses, the maximum observed
complexation-induced shifts ([ppm], ‡ˆ downfield), Ddsat and Ddmaxobs, of the receptor HÀC(4) and HÀC(9)
signals monitored during the titration (for the numbering, see Fig. 1).
Sugar/Solventa)
Ka
)
]
DG0
[kcal molÀ1
Ddsat (Ddmaxobs) HÀC(4)
Ddsat(Ddmaxobs) HÀC(9)
b
[mÀ1
]
[ppm]
[ppm]
53/CD3CN
54/CD3CN
55/CD3CN
55/CD3CNc)
55/CDCl3
370
310
570
130
1090
À 3.5
À 3.4
À 3.8
À 2.9
À 4.1
‡ 0.040 (‡ 0.032)
‡ 0.042 (‡ 0.033)
‡ 0.041 (‡ 0.033)
‡ 0.022 (‡ 0.012)
‡ 0.048 (‡ 0.043)
‡ 0.054 (‡ 0.043)
‡ 0.054 (‡ 0.043)
‡ 0.050 (‡ 0.044)
‡ 0.024 (‡ 0.013)
‡ 0.056 (‡ 0.051)
b
a) Host concentration was constant at 1.0 mm, guest concentration varied between 0.5 and 12.5 mm.
Uncertainties in Ka estimated at Æ10%. ) Addition of 2% MeOD.
)
c
1
2.3.2. H-NMR Binding Studies with Receptors Featuring Two 1,1'-Binaphthalene-
2,2-diyl-Phosphate Recognition Sites. Dendritic receptors with two ionic H-bonding
sites were expected to exhibit higher association strength and substrate selectivity [21].
On the other hand, nearly free rotation about the buta-1,3-diynediyl or p-phenylene
spacer between the two 1,1'-binaphthalene moieties enables these systems to adopt a
large number of conformations. Cooperative binding of one sugar molecule to both
phosphodiester sites ± with formation of a 1:1 host-guest complex ± can only take place
in the ꢀsynꢁ-conformation, in which the two 1,1'-binaphthalene moieties are oriented in
the same direction. Computer modeling [41] and CPK (Corey-Pauling-Koltum) model
examinations indicated that the ꢀsynꢁ-conformers of the receptors with a buta-1,3-
diynediyl bridge feature an appropriately sized cleft to accommodate monosaccharide
guests through ionic H-bonding to both phosphodiester moieties. Previous studies with
macrocyclic receptors, in which the buta-1,3-diynediyl-bridged 1,1'-binaphthalene-2,2'-
diyl-phosphate sites are forced into the ꢀsynꢁ-conformation, further corroborated these
expectations [21a]. In contrast, ꢀantiꢁ-type conformations, with the two phosphodiester
sites pointing in opposite directions, could favor formation of 1:2 host-guest
complexes. Even the formation of complexes in which two receptor molecules
surround one guest molecule could not be excluded a priori.

1362
Helvetica Chimica Acta ± Vol. 83 (2000)
2.3.2.1. Binding Studies with Reference Receptors. In 1H-NMR binding titrations at
constant concentration of receptors (S,S)-31 and (S,S)-32, the resonance of the
acetylenic H-atom was conveniently monitored (Table 5). In some titrations, complex-
ation-induced downfield shifts of the binaphthalene resonances (HÀC(4), HÀC(4'),
and HÀC(8); for numbering, see Fig. 2) could also be evaluated, providing similar
thermodynamic quantities.
Table 5. Association Constants Ka [mÀ1] and Complexation Free Enthalpies DG0 [kcal molÀ1] from 1H-NMR
Binding Titrations (500 MHz) for 1 : 1 Complexes of Receptors (S,S )-31 and (S,S )-32 with Monosaccharides 53 ±
55 in CD3CN (300 K). Also shown are the calculated and, in parentheses, the maximum observed complexation-
induced shifts ([ppm], ‡ˆ downfield), Ddsat and Ddmaxobs, of the ethynyl resonance of the receptor which was
monitored during the titration.
Sugara)
Receptor
Ka b) [mÀ1
]
DG0 [kcal molÀ1
]
Ddsat (Ddmaxobs) [ppm]
53
54
55
53
54
55
(S,S)-31
(S,S)-31
(S,S)-31
(S,S)-32
(S,S)-32
(S,S)-32
200
150
350
210
260
280
À 3.1
À 3.0
À 3.5
À 3.2
À 3.3
À 3.4
‡ 0.065 (‡ 0.044)
‡ 0.076 (‡ 0.045)
‡ 0.066 (‡ 0.054)
‡ 0.059 (‡ 0.042)
‡ 0.065 (‡ 0.051)
‡ 0.057 (‡ 0.038)
b
a) Host concentration was constant at 0.5 mm, guest concentration varied between 0.3 and 12.5 mm.
Uncertainty in Ka estimated at 10%.
)
The two receptors (S,S)-31 and (S,S)-32 form 1:1 complexes of comparable
stability with octyl glucosides in CD3CN (Ka ˆ 150 ± 350 mÀ1, DG0 ˆ À3.0 to
À3.5 kcal molÀ1; Table 5). The association constants are increased by a factor of about
two, as compared to those determined for the corresponding complexes of the non-
dendritic receptor (S)-4 featuring only one phosphodiester site (Table 1). The
substrate selectivity remained low in all cases. Competing higher-order complexation
prevented the determination of the stability of 1:1 host-guest complexes in CDCl3.
2.3.2.2. Binding Studies with the Dendritic Receptors. The dendritic receptors G-2-
(S,S)-41 and G-1-(S,S)-43 with buta-1,3-diynediyl spacers showed good solubility in
CD3CN (up to 5 mm) and did not aggregate appreciably at concentrations below 5 mm
(1H-NMR dilution experiment with G-2-(S)-41). Complexation-induced shifts ob-
served in the 1H-NMR spectra in CD3CN indicated that the receptors were interacting
with the octyl glucosides. Job-plot analyses were subsequently performed with receptor
G-2-(S,S)-41 and octyl glucoside 55 in order to shed light on the stoichiometry of the
associations formed. Due to only very modest changes of Dd/xsugar or Dd/xhost, the curves
exhibited flat shapes weakly indicating a maximum around 0.5. This result was
considered to be a first, yet inconclusive, indication for a 1:1 host-guest complexation
mode.
Liquid-liquid extractions with receptor G-2-(S,S)-41 (1.0 mm in CDCl3 or CD3CN)
and d-glucose (40 mm in H2O), in which the mixture was exposed for 15 min to an
ultrasonic bath at 208, resulted in no extraction of the sugar into the organic phase
(1H-NMR). Under the same experimental conditions (receptor concentration 1.0 mm),
however, solid d-glucose was solubilized in both CDCl3 and CD3CN. A strong
broadening of all signals was observed in the 1H-NMR spectra of the organic solutions

Helvetica Chimica Acta ± Vol. 83 (2000)
1363
after extraction, which prevented any analysis of stoichiometry and host-guest bonding.
Therefore, the solvent was evaporated, and the resulting solid was redissolved in
(CD3)2SO. In this solvent, the interaction between host and guest that caused the
signal broadening became very weak, and the amount of extracted sugar could be
1
determined by integration of the H-NMR resonances of the binding partners. The
results indicated that 1.0 equiv. of d-glucose was extracted into the CD3CN solution,
whereas, under the same conditions, 2.0 equiv. of the sugar were extracted into the
CDCl3 solution.
1H-NMR Binding titrations with G-2-(S,S)-41 and octyl glucosides 53 ± 55 were
subsequently carried out at 300 K in dry CD3CN, CDCl3, and CD3CN/MeOD 98 :2.
Highly resolved spectra were obtained, and the complexation-induced downfield shift
of the signals of the 1,1'-binaphthalene protons HÀC(4) and HÀC(4') could be readily
monitored during the titrations. However, nonlinear least-squares curve fitting to a 1:1
host-guest complexation model with Associate V. 1.6 was not successful. It became clear
that higher-order association occurred predominantly. Attempts to further analyze the
situation with the program Specfit V.2.10 [42], which is capable of fitting data from
multiple binding equilibria, failed. Disappointingly, a similar situation was encountered
in binding studies with G-2-(S,S)-42 and G-1-(S,S)-43. All attempts to determine
concentration conditions for standard or inverse titrations, under which one single
defined host-guest complexation stoichiometry would prevail, failed. The absence of
defined 1:1 host-guest association clearly contrasts with the preference of the non-
dendritic reference compounds (S,S)-31 and (S,S)-32 to form 1:1 host-guest complexes
(Table 5). It must, therefore, be concluded that the dendritic wedges prevent 1:1 host-
guest complexation by the dendroclefts. We propose that the ꢀsynꢁ-conformations of
these receptors, in which the two phosphodiester moieties can bind cooperatively to
one sugar molecule, are strongly disfavored due to repulsive intramolecular inter-
actions between the dendritic wedges.
3. Conclusions. ± Two classes of optically active, cleft-type dendritic receptors
(dendroclefts) for carbohydrate recognition were constructed by efficient, high-yielding
routes. The first series contains a 1,1'-binaphthalene-2,2'-diyl phosphate core embedded
Â
into Frechet-type dendrons of first to third generation. The second series features
similar dendritic wedges (up to the second generation), whereas the core consists of
two 1,1'-binaphthalene-2,2'-diyl phosphate moieties bridged by buta-1,3-diynediyl or p-
1
phenylene spacers. H-NMR Binding studies (300 K) showed that bidentate ionic H-
bonding between the phosphodiester moieties and the OH-groups of octyl glucosides
represents the predominant binding mode in the complexes that form in CD3CN or less
polar solvents such as CDCl3. Interactions between the apolar surfaces of the sugar and
the aromatic rings of the dendritic wedges provide a minor (up to a factor of ca. 3 in Ka)
yet clearly identifiable contribution to the overall binding free enthalpy in CD3CN. The
dendritic receptors G-1-(S)-1, G-2-(S)-2, and G-3-(S)-3 with a single 1,1'-binaphtha-
lene core predominantly form complexes of 1:1 host-guest stoichiometry with octyl
glucosides, and association strength was readily evaluated. Host-guest binding affinity
increased upon changing from non-dendritic reference receptors to the first- and
second-generation dendroclefts, but decreased at the third-generation level, due to
steric hindrance of the core H-bonding site by the bulky dendritic wedges. The dendritic

1364
Helvetica Chimica Acta ± Vol. 83 (2000)
receptors G-2-(S,S)-41, G-2-(S,S)-42, and G-1-(S,S)-43 with two 1,1'-binaphthalene
moieties at the core underwent complex higher-order association, and experimental
conditions, under which 1:1 complexation would be predominant, could not be worked
out. In contrast, the reference compounds (S,S)-31 and (S,S)-32, which feature similar
cores but lack the dendritic wedges, form defined 1:1 host-guest complexes. We,
therefore, conclude that unfavorable intramolecular steric interactions between the
dendritic wedges in G-2-(S,S)-41, G-2-(S,S)-42, and G-1-(S,S)-43 prevent these
receptors from adopting the ꢀsynꢁ-conformation, in which the two 1,1'-binaphthalene-
2,2'-diyl phosphate sites converge to interact with a single sugar molecule under
formation of a 1:1 complex. Overall, this study indicates that dendritic cleft-type
receptors are too flexible to form high-affinity, high-selectivity complexes with
monosaccharides. The dendritic wedges are not effective in providing apolar
interactions and solvophobic driving forces required for binding carbohydrates in
protic solvents. Therefore, our efforts aimed at achieving carbohydrate recognition by
synthetic receptors in protic solvents, and in particular in H2O, will be continued with
the design and synthesis of more elaborate systems that feature multiple H-bonding
sites converging into a spherical, highly preorganized macrocyclic recognition site of
reduced polarity at the core of dendrimers.
This work was supported by a grant from the ETH research council and F. Hoffmann-La Roche, Basel. A. B.
Â
is grateful for a doctoral fellowship of the Fonds der Chemischen Industrie (Kekule-Stipendium). We thank Dr.
Monika Sebova for NMR measurements and Sven Meier for his help with the receptor synthesis.
Experimental Part
General. All reactions were carried out under N2. Solvents and reagents were reagent-grade and used
without further purification unless otherwise stated. THF and Et2O were freshly distilled from sodium
benzophenone ketyl. Evaporation in vacuo was conducted at H2O aspirator pressure. Column chromatography
(CC): SiO2 60 (230 ± 400 mesh, 0.040 ± 0.063 mm) from E. Merck (for products containing MOM-ether
protecting groups) or Fluka; visualization by UV light. Prep. gel-permeation chromatography (GPC): Bio-
Beads SX-1 or SX-3 from Bio-Rad, eluent CH2Cl2 unless otherwise stated; detection at 300 nm by UV on an
anal. GPC apparatus from Merck Hitachi. M.p.: Büchi SMP-20; uncorrected. Optical rotation ([a]rD:t: ): Perkin-
Elmer 241 polarimeter with a 1-dm cell at the Na-D line (l ˆ 589 nm) at r.t. The concentration c is given in
g/100 ml. CHCl3 was used as solvent unless otherwise stated. IR Spectra (cmÀ1): Perkin-Elmer 1600-FT IR. NMR
Spectra: Bruker AMX 500 or AMX 400, and Varian Gemini 300 or 200 at 296 or 300 K, with solvent peak as
reference. MS (m/z (%)): EI: VG TRIBRID spectrometer at 70 eV; FAB: VG ZAB2-SEQ spectrometer with 3-
nitrobenzyl alcohol (NOBA) as matrix; MALDI-TOF: Bruker Reflex spectrometer with 2-(4-hydroxyphenyl-
azo)benzoic acid (HABA), a-cyano-4-hydroxycinnamic acid (CCA), 2,4,6-trihydroxyacetophenone/diammo-
nium citrate (THA/citrate) 2 :1 or 1,8,9-trihydroxyanthracene (dithranol) as matrix; positive-ion mode unless
otherwise stated. Elemental analyses were performed by the Mikrolabor at the Laboratorium für Organische
Chemie, ETH-Zürich.
1H-NMR Binding Titrations. Quantitative binding data (Ka, DG0, Ddsat) were determined by nonlinear
least-squares curve-fitting of 1H-NMR titration data (500 MHz, 300 K) with the program Associate V.1.6 [40].
Commercially available guests 53 and 55 were used without further treatment. Octyl pyranoside 54 was
prepared according to published procedures [43]. Titration samples were prepared by adding a soln. of guest in
portions via microsyringe to the septum-capped NMR tube containing the host at constant concentration. After
each addition, a 1H-NMR spectrum was recorded. In inverse titrations, constant guest and variable host
concentrations were applied. Specific concentrations used in the titrations are included in the footnotes to
Tables 1 ± 5.
1,3-Bis(benzyloxy)-5-iodobenzene (G-1-8). A mixture of 5-iodobenzene-1,3-diol (1.25 g, 5.3 mmol),
PhCH2Br (1.81 g, 1.15 ml, 10.6 mmol), [18]crown-6 (0.42 g, 1.6 mmol), and K2CO3 (2.20 g, 15.9 mmol) in dry
acetone (100 ml) was heated under N2 and vigorous stirring to 558 for 24 h. The solvent was evaporated, and the

Helvetica Chimica Acta ± Vol. 83 (2000)
1365
residue was dissolved in H2O (40 ml) and CH2Cl2 (50 ml). The aq. layer was extracted with CH2Cl2 (2 Â 50 ml),
the combined org. phases were dried (MgSO4), and the solvent was evaporated in vacuo. CC (SiO2; hexane/
AcOEt 6 :1) yielded G-1-8 (2.1 g, 95%). White powder. M.p. 578. IR (KBr): 3067w, 3032m, 2998w, 2930w,
2878m, 1592s, 1568s, 1491m, 1444m, 1425m, 1377s, 1341w, 1324m, 1277s, 1239m, 1215m, 1049m, 1028m, 986m.
1H-NMR (300 MHz, CDCl3): 5.08 (s, 4 H); 6.60 (t, J ˆ 2.5, 1 H); 7.01 (d, J ˆ 2.5, 2 H); 7.33 ± 7.49 (m, 10 H).
13C-NMR (75 MHz, CDCl3): 70.41; 94.26; 102.41; 117.28; 127.81; 128.42; 128.91; 136.63; 160.57. FAB-MS: 417
‡
(100, MH ). Anal. calc. for C20H17IO2 (416.26): C 57.71, H 4.12, O 7.69; found: C 57.80, H 4.26, O 7.77.
1,3-Bis[3,5-bis(benzyloxy)benzyloxy]-5-iodobenzene (G-2-9). A mixture of 5-iodobenzene-1,3-diol (1.9 g,
7.8 mmol), 6 [22] (6.3 g, 16.5 mmol), [18]crown-6 (0.41 g, 1.6 mmol), and K2CO3 (4.3 g, 31.4 mmol) in dry
acetone (140 ml) was heated under N2 and vigorous stirring to 558 for 24 h. Workup as described for G-1-8,
followed by CC (SiO2; CH2Cl2/hexane 3 :1) yielded G-2-9 (6.0 g, 90%). White powder. M.p. 1168. IR (KBr):
3011w, 2889w, 1592s, 1450m, 1369s, 1328m, 1297m, 1156s. 1H-NMR (200 MHz, CDCl3): 4.90 (s, 4 H); 5.02 (s,
8 H); 6.50 (t, J ˆ 2.2, 1 H); 5.56 (t, J ˆ 2.2, 2 H); 6.62 (d, J ˆ 2.2, 4 H); 6.92 (d, J ˆ 2.2, 2 H); 7.26 ± 7.42 (m, 20 H).
13C-NMR (100 MHz, CDCl3): 70.09; 70.14; 94.03; 101.71; 102.15; 106.37; 117.04; 127.54; 128.02; 128.59; 136.73;
‡
‡
138.72; 160.11; 160.19. MALDI-TOF-MS (2,5-DHB): 880 (20, [M ‡ K] ), 864 (73, [M ‡ Na] ), 841 (100,
‡
MH ). Anal. calc. for C48H41IO6 (840.76): C 68.57, H 4.92; found: C 68.64, H 5.03.
1,3-Bis{3,5-bis[3,5-bis(benzyloxy)benzyloxy]benzyloxy}-5-iodobenzene (G-3-10). A mixture of 5-iodo-
benzene-1,3-diol (0.47 g, 2.0 mmol), 7 (3.55 g, 4.4 mmol), [18]crown-6 (140 mg, 0.5 mmol), and K2CO3 (1.38 g,
9.0 mmol) in dry MeCN/acetone 1:1 (100 ml) was heated under N2 and vigorous stirring to 558 for 3 d. Workup
as described for G-1-8, followed by CC (SiO2; CH2Cl2/hexane 3 :1) yielded G-3-10 (2.7 g, 79%). White solid.
M.p. 538. IR (KBr): 3027m, 2918w, 2864m, 1595s, 1449m, 1374m, 1342w, 1319w, 1292m, 1156s, 1051m. 1H-NMR
(300 MHz, CDCl3): 4.90 (s, 4 H); 4.96 (s, 8 H); 5.01 (s, 16 H); 6.53 ± 6.58 (m, 7 H); 6.62 (d, J ˆ 2.4, 4 H); 6.67 (d,
J ˆ 2.1, 8 H); 6.95 (d, J ˆ 2.1, 2 H); 7.26 ± 7.42 (m, 40 H). 13C-NMR (125 MHz, CDCl3): 70.01; 70.11 (2Â); 94.04;
101.63; 101.73; 102.17; 106.38; 106.44; 117.05; 127.53; 127.98; 128.56; 136.77; 138.72; 139.17; 160.09; 160.13;
‡
160.17. MALDI-TOF-MS (HABA): 1712 ([M ‡ Na] ). Anal. calc. for C104H89IO14 (1689.74): C 73.93, H 5.31,
O 13.26; found: C 73.77, H 5.15, O 13.04.
1,3-Bis(3,5-bis{2-[2-(2-methoxyethoxy)ethoxy]ethoxy}benzyloxy)-5-iodobenzene (G-1-11). To 5-iodoben-
zene-1,3-diol (0.30 g, 1.29 mmol) and 12 (1.11 g, 2.68 mmol) in acetone (63 ml), K2CO3 (0.457 g, 3.31 mmol),
and [18]crown-6 (69 mg, 0.26 mmol) were added, and the mixture was heated under N2 to 608. After 20 h, the
mixture was cooled to 208 and filtered through Celite and SiO2. Evaporation in vacuo and GPC (Bio-Beads
SX-3) afforded G-1-11 (586 mg, 43%). Highly viscous oil. IR (neat): 3087w, 2938s, 2875s, 2724w, 1962w, 1754w,
1722w, 1684w, 1596s, 1572m, 1448s, 1374m, 1348m, 1321m, 1198m, 1172s, 1110s, 1070s, 1027m, 995m, 947m,
841m, 718w, 680m. 1H-NMR (200 MHz, CDCl3): 3.39 (s, 12 H); 3.54 ± 3.59 (m, 8 H); 3.65 ± 3.77 (m, 24 H); 3.84 ±
3.88 (m, 8 H); 4.10 ± 4.15 (m, 8 H); 4.92 (s, 4 H); 6.47 (t, J ˆ 2.0, 2 H); 6.53 ± 6.58 (m, 5 H); 6.95 (d, J ˆ 2.2, 2 H).
13C-NMR (75 MHz, CDCl3): 59.15; 67.64; 69.80; 70.23; 70.72; 70.80; 70.96; 72.08; 94.19; 101.46; 102.35; 106.28;
‡
117.18; 138.84; 160.44 (2Â). FAB-MS: 1065 (100, M ). Anal. calc. for C48H73IO18 (1065.01): C 54.13, H 6.91;
found: C 54.13, H 6.86.
(S)-3,3'-Diethynyl-1,1'-binaphthalene-2,2'-diol ((S)-14). To (S)-13 (100 mg, 0.24 mmol) in THF/MeOH 1:1
(200 ml), conc. HCl (37%, 350 ml) was added. The soln. was stirred for 4 h under N2 at 208, then H2O (200 ml)
was added. The aq. phase was extracted with CH2Cl2 (2 Â 100 ml), and the combined org. phases were dried
(Na2SO4) and concentrated to give crude (S)-14 (91 mg, 99%). 1H-NMR (200 MHz, CDCl3): 3.33 (s, 2 H); 5.75
(s, 2 H); 7.10 ± 7.15 (m, 2 H); 7.31 ± 7.41 (m, 4 H); 7.83 ± 7.88 (m, 2 H); 8.21 (s, 2 H).
Tetrabutylammonium (‡)-(S)-3,3'-Diethynyl-1,1'-binaphthalene-2,2'-diyl Phosphate ((‡)-(S)-4). To (S)-14
(0.11 g, 0.24 mmol) in dry CH2Cl2 (50 ml), POCl3 (0.16m soln. in CH2Cl2, 4.8 ml, 0.53 mmol) and Et3N (0.73 g,
1.0 ml, 7.2 mmol) were added at 208 under N2, and the soln. was stirred for 3 h. After evaporation in vacuo, THF/
H2O 1:1 (40 ml) was added, and the mixture was stirred for 12 h at 408. CH2Cl2 (80 ml) and H2O (80 ml) were
added, and the separated org. phase was washed with H2O (2 Â 60 ml), dried (Na2SO4), and concentrated.
‡
Recrystallization (toluene), followed by ion-exchange chromatography (Dowex 50WX8, Bu4N ; CH2Cl2/MeCN
1:1), provided (S)-4 (58 mg, 38% starting from (S)-13). Yellow solid. M.p. > 2408. [a]rD:t: ˆ ‡223.5 (c ˆ 0.5,
CHCl3). IR (KBr): 3310w, 3167w, 2956m, 2867w, 2100m, 1483m, 1306s, 1450m, 1236m, 1111s, 1097s, 903m, 767m.
1H-NMR (200 MHz, CD3CN): 0.93 (t, J ˆ 7.2, 12 H); 1.22 ± 1.63 (m, 16 H); 3.00 (m, 8 H); 3.60 (s, 2 H); 7.13 ± 7.17
(m, 2 H); 7.23 ± 7.31 (m, 2 H); 7.40 ± 7.48 (m, 2 H); 7.91 ± 7.95 (m, 2 H); 8.22 (s, 2 H). 13C-NMR (50 MHz,
CD3CN): 13.88; 20.42; 24.43; 59.48; 81.65; 82.74; 117.94; 123.80; 126.43; 127.52; 128.33; 129.47; 131.14; 133.76;
135.82; 151.58 (d, J(31P, 13C) ˆ 9.3). 31P-NMR (121 MHz, CD3CN): 5.36. ESI-MS (negative-ion mode): 395 (100,
[M À Bu4N]À). Anal. calc. for C40H48NO4P ´ H2O (655.82): C 73.26, H 7.68, N 2.14; found: C 73.16, H 7.67,
N 2.25.

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Helvetica Chimica Acta ± Vol. 83 (2000)
(‡)-(S)-2,2'-Bis(methoxymethoxy)-3,3'-bis(2-phenylethynyl)-1,1'-binaphthalene ((‡)-(S)-15). A degassed
soln. of (S)-13 (100 mg, 0.24 mmol) in abs. THF (2 ml) was added slowly (10 min) to a degassed soln. of PhI
(0.10 ml, 0.92 mmol), [PdCl2(PPh3)2] (12 mg, 5 mol-%), and CuI (3 mg, 5 mol-%) in dry THF (4 ml) and dry (i-
Pr)2NH (3 ml) at 408, and the mixture was stirred for 2 h at 408. Sat. aq. NaCl soln. (20 ml) and CH2Cl2 (30 ml)
were added, the phases were separated, and the aq. phase was extracted with CH2Cl2 (30 ml). The combined
org. phases were dried (Na2SO4) and concentrated. CC (SiO2; hexane/AcOEt 6 :1, containing 0.5% Et3N)
yielded (S)-15 (134 mg, 97%). White foam. M.p. 818. [a]rD:t: ˆ ‡197.1 (c ˆ 1.0, CHCl3). IR (KBr): 3058m, 2951m,
2925m, 2818w, 2216w, 1594m, 1492s, 1443m, 1426m, 1390m, 1359m, 1332w, 1257w, 1226m, 1199m, 1157s, 1097m,
1062s, 1013m, 972s, 916m. 1H-NMR (300 MHz, CDCl3): 2.53 (s, 6 H); 4.97 (d, AB, J ˆ 6.3, 2 H); 5.21 (d, AB, J ˆ
6.3, 2 H); 7.29 ± 7.37 (m, 10 H); 7.41 ± 7.47 (m, 2 H); 7.55 ± 7.58 (m, 4 H); 7.87 (d, J ˆ 8.1, 2 H); 8.24 (s, 2 H).
13C-NMR (75 MHz, CDCl3): 56.19; 86.65; 93.92; 99.07; 117.52; 123.46; 125.79; 126.13; 126.82; 127.47; 127.83;
‡
128.68; 128.72; 130.59; 131.82; 134.05; 134.46; 153.35. FAB-MS: 574 (100, M ). Anal. calc. for C40H30O4 ´ 0.5H2O
(580.67): C 82.31, H 5.35; found: C 82.65, H 5.39.
(‡)-(S)-3,3'-Bis(2-phenylethynyl)-1,1'-binaphthalene-2,2'-diol ((‡)-(S)-16). To (S)-15 (170 mg, 0.30 mmol)
in THF (100 ml), conc. HCl (37%, 250 ml) in MeOH (100 ml) was added, and the soln. was stirred for 12 h under
N2 at 208. H2O (200 ml) and CH2Cl2 (200 ml) were added, the aq. phase was extracted with CH2Cl2 (100 ml), the
combined org. phases were dried (Na2SO4), and concentration gave crude (S)-16 (110 mg, 75%). Oil. 1H-NMR
(300 MHz, CDCl3): 5.91 (s, 2 H); 7.19 (d, J ˆ 8.4, 2 H); 7.26 ± 7.40 (m, 10 H); 7.57 ± 7.60 (m, 4 H); 7.87 (d, J ˆ 7.5,
2 H); 8.21 (s, 2 H).
Tetrabutylammonium (‡)-(S)-3,3'-Bis(2-phenylethynyl)-1,1'-binaphthalene-2,2'-diyl Phosphate ((‡)-(S)-
5). To crude (S)-16 (100 mg, 0.17 mmol) in dry CH2Cl2 (35 ml), POCl3 (0.2m soln. in CH2Cl2, 1.9 ml, 0.38 mmol)
and Et3N (0.53 g, 0.73 ml, 5.2 mmol) were added at 208 under N2, and the soln. was stirred for 6 h. After
evaporation in vacuo, THF/H2O 1:1 (30 ml) was added, and the mixture was stirred for 12 h at 308. CH2Cl2
(50 ml) and H2O (30 ml) were added, the separated org. phase was washed with H2O (2 Â 30 ml), dried
(Na2SO4), and concentrated. CC (SiO2; CH2Cl2/Et3N 98 :3, followed by ion-exchange chromatography (Dowex
‡
50WX8, Bu4N ; CH2Cl2/MeCN 1 :1), provided (S)-5 (58 mg, 54%). M.p. 2398. [a]rD:t: ˆ ‡287.1 (c ˆ 0.5, CHCl3).
IR (neat): 3389m (br.), 3056m, 2954m, 2934m, 2867w, 2211w, 1598m, 1490s, 1439m, 1420m, 1378w, 1361w, 1299s,
1213m, 1152w, 1109s, 1096s, 1091w, 963w, 918m. 1H-NMR (500 MHz, CD3CN): 0.91 (t, J ˆ 7.2, 12 H); 1.25 ± 1.32
(m, 8 H); 1.48 ± 1.55 (m, 8 H); 2.98 ± 2.01 (m, 8 H); 7.20 (d, J ˆ 8.2, 2 H); 7.25 ± 7.29 (m, 2 H); 7.40 ± 7.46 (m, 8 H);
7.63 ± 7.65 (m, 4 H); 7.95 (d, J ˆ 8.2, 2 H); 8.23 (s, 2 H). 13C-NMR (125 MHz, CD3CN): 13.70; 20.21; 24.20; 59.12;
87.84; 93.71; 118.59; 123.52 (d, J(31P, 13C) ˆ 2.3); 124.41; 126.00; 127.24; 127.72; 129.14; 129.42; 129.57; 130.92;
132.48; 133.26; 134.22; 151.13 (d, J(31P, 13C) ˆ 9.8). 31P-NMR (121 MHz, CD3CN): 6.10. ESI-MS (negative-ion
mode): 547 (100, [M À Bu4N]À). Anal. calc. for C52H56NO4P ´ 0.5H2O (799.01): C 78.17, H 7.19; N 1.75, O 9.01,
P 3.88; found: C 78.11, H 7.37, N 1.77, O 8.48, P 3.91.
(‡)-(S)-3,3'-Bis{2-[3,5-bis(benzyloxy)phenyl]ethynyl}-2,2'-bis(methoxymethoxy)-1,1'-binaphthalene (G-1-
(‡)-(S)-17). A degassed soln. of (S)-13 (50 mg, 0.12 mmol) in dry THF (2 ml) was added slowly (30 min) to a
degassed soln. of G-1-8 (110 mg, 0.26 mmol), [PdCl2(PPh3)2] (4.0 mg, 4 mol-%), and CuI (0.9 mg, 4 mol-%) in
abs. THF (1 ml) and dry (i-Pr)2NH (3 ml). After stirring at 408 for 5 h, sat. aq. NaCl soln. (10 ml) and CH2Cl2
(20 ml) were added. The phases were separated, and the aq. phase was extracted with CH2Cl2 (15 ml). The
combined org. phases were dried (Na2SO4) and concentrated. CC (SiO2; CH2Cl2/toluene 1:2 ! 1 :1, containing
0.5% Et3N) afforded G-1-(‡)-(S)-17 (100 mg, 85%). White foam. M.p. 688. [a]rD:t: ˆ ‡82.1 (c ˆ 0.5, CHCl3). IR
(KBr): 3059w, 3033w, 2922s, 2846m, 2236w, 1585s, 1493w, 1454m, 1430m, 1373m, 1349m, 1318w, 1244m, 1211w,
1159s, 1100w, 1056m, 980m, 925w, 908w. 1H-NMR (500 MHz, CDCl3): 2.51 (s, 6 H); 4.93 (d, AB, J ˆ 6.3, 2 H);
5.06 (s, 8 H); 5.17 (d, AB, J ˆ 6.3, 2 H); 6.64 (t, J ˆ 2.4, 2 H); 6.82 (d, J ˆ 2.3, 4 H); 7.16 ± 7.47 (m, 26 H); 7.86 (d,
J ˆ 8.1, 2 H); 8.23 (s, 2 H). 13C-NMR (75 MHz, CDCl3): 56.19; 70.36; 86.36; 93.85; 93.85; 99.13; 103.87; 110.79;
117.36; 124.82; 125.82; 126.11; 126.82; 127.53; 127.75; 127.84; 128.31; 130.58; 134.09; 134.56; 136.89; 153.39;
‡
160.08. FAB-MS: 999 (100, M ). Anal. calc. for C68H54O8 ´ 0.5H2O (1008.19): C 81.08, H 5.50; found: C 80.92,
H 5.59.
(‡)-(S)-3,3'-Bis{2-[3,5-bis(benzyloxy)phenyl]ethynyl}-1,1'-binaphthalene-2,2'-diol (G-1-(‡)-(S)-18). To
G-1-(‡)-(S)-17 (90 mg, 0.09 mmol) in THF (35 ml), conc. HCl (37%, 100 ml) in MeOH (35 ml) was added,
and the soln. was stirred under N2 at 208 for 7 h. After addition of H2O (60 ml), the aq. phase was extracted with
CH2Cl2 (2 Â 70 ml), and the combined org. phases were dried (Na2SO4) and concentrated. CC (SiO2; CH2Cl2/
toluene 1:5, containing 0.5% Et3N) afforded G-1-(‡)-(S)-18 (65 mg, 79%). Foam. M.p. 888. [a]rD:t: ˆ ‡56.3 (c ˆ
0.5, CHCl3). IR (neat): 3491s (br.), 3063w, 3023w, 2924w, 2854w, 2219w, 1593s, 1586s, 1495w, 1451w, 1426m,
1376w, 1351w, 1262m, 1222m, 1152s, 1048m, 1022w. 1H-NMR (500 MHz, CDCl3): 5.06 (s, 8 H); 5.84 (s, 2 H); 6.68
(t, J ˆ 2.1, 2 H); 6.85 (d, J ˆ 2.1, 4 H); 7.20 (d, J ˆ 7.8, 2 H); 7.28 ± 7.47 (m, 24 H); 7.88 (d, J ˆ 7.5, 2 H); 8.21 (s,

Helvetica Chimica Acta ± Vol. 83 (2000)
1367
2 H). 13C-NMR (100 MHz, CDCl3): 70.38; 83.82; 96.33; 104.30; 110.90; 112.34; 113.70; 124.04; 124.66; 127.54;
‡
127.76; 128.25; 128.36; 128.51; 128.91; 129.01; 133.70; 134.10; 136.84; 151.14; 160.15. FAB-MS: 911 (100, M ).
‡
HR-FAB-MS: 911.3298 (M , C64H46O6; calc. 911.3294).
Tetrabutylammonium (‡)-(S)-3,3'-Bis{2-[3,5-bis(benzyloxy)phenyl]ethynyl}-1,1'-binaphthalene-2,2'-diyl
Phosphate (G-1-(‡)-(S)-1). To G-1-(‡)-(S)-18 (45 g, 0.05 mmol) in dry CH2Cl2 (10 ml), POCl3 (0.2m soln. in
CH2Cl2, 0.55 ml, 0.11 mmol) and Et3N (135 mg, 195 ml, 1.4 mmol) were added at 208 under N2, and the soln. was
stirred for 3 h. Evaporation in vacuo and addition of THF/H2O 1 :1 (10 ml) provided a mixture, which was
stirred for 12 h at 308. CH2Cl2 (20 ml) and H2O (30 ml) were added, the separated org. phase was washed with
H2O (2 Â 20 ml), dried (Na2SO4), and concentrated. CC (SiO2; CH2Cl2/Et3N 99 :1), followed by ion-exchange
‡
chromatography (Dowex 50WX8, Bu4N , CH2Cl2/MeCN 1:1), afforded G-1-(‡)-(S)-1 (43 mg, 71%). Yellow
foam. M.p. 878. [a]Dr:t: ˆ ‡194.6 (c ˆ 0.5, CHCl3). IR (neat): 3060w, 3025w, 2955m, 2217w, 1587s, 1492w, 1431m,
1374m, 1292m, 1253w, 1157s, 1101m, 1053m. 1H-NMR (500 MHz, CDCl3): 0.73 (t, J ˆ 7.3, 12 H); 1.11 ± 1.14 (m,
8 H); 1.23 ± 1.28 (m, 8 H); 2.89 (t, J ˆ 9.05, 8 H); 5.03 (s, 8 H); 6.59 (t, J ˆ 2.4, 2 H); 6.94 (d, J ˆ 2.4, 4 H); 7.17 ±
7.23 (m, 2 H); 7.29 ± 7.43 (m, 24 H); 7.81 (d, J ˆ 8.2, 2 H); 8.13 (s, 2 H). 13C-NMR (125 MHz, CD3CN): 13.56;
19.46; 23.64; 58.16; 70.16; 86.85; 92.99; 103.02; 110.98; 117.72; 122.67; 122.68; 124.75; 125.52; 126.33; 126.79;
127.57; 127.88; 127.93; 128.50; 130.05; 132.51; 133.61; 136.71; 159.56. 31P-NMR (121 MHz, CDCl3): 4.71. FAB-
‡
‡
‡
‡
MS: 1457 (49, [M ‡ Bu4N] ), 1215 (21, MH ), 973 (6, [MH2 À Bu4N] ), 243 (100, Bu4N ). HR-FAB-MS:
‡
972.2848 ([MH À Bu4N] , C64H45O8P; calc. 972.2852).
(‡)-(S)-3,3'-Bis(2-{3,5-bis[3,5-bis(benzyloxy)benzyloxy]phenyl}ethynyl)-2,2'-bis(methoxymethoxy)-1,1'-bi-
naphthalene (G-2-(‡)-(S)-19). To a degassed soln. of (S)-13 (0.2 g, 0.47 mmol) in abs. THF (12 ml) and dry (i-
Pr)2NH (6 ml), [PdCl2(PPh3)2] (16.6 mg, 5 mol-%), CuI (4.5 mg, 5 mol-%), and G-2-9 (0.80 g, 0.95 mmol) were
added, and the mixture was heated to 408 for 12 h. Sat. aq. NaCl soln. (60 ml) and CH2Cl2 (70 ml) were added,
the phases were separated, and the aq. phase was extracted with CH2Cl2 (2 Â 60 ml). The combined org. phases
were dried (Na2SO4), filtered through SiO2 and Celite, and concentrated. GPC (Bio-Beads SX-1) afforded G-2-
(‡)-(S)-19 (0.62 g, 71%). Highly viscous oil. [a]rD:t: ˆ ‡96.7 (c ˆ 0.5, CHCl3). IR (KBr): 3031w, 2869w, 2214w,
1593s, 1506s, 1449m, 1152s, 1053m, 736m, 696m. 1H-NMR (400 MHz, CDCl3): 2.48 (s, 6 H); 4.92 (d, AB, J ˆ 6.2,
2 H); 4.96 (s, 8 H); 5.01 (s, 16 H); 5.16 (d, AB, J ˆ 6.2, 2 H); 6.55 (t, J ˆ 2.3, 4 H); 6.58 (t, J ˆ 2.3, 2 H); 6.66 (d,
J ˆ 2.3, 8 H); 6.78 (d, J ˆ 2.3, 4 H); 7.21 ± 7.42 (m, 46 H); 7.83 ± 7.85 (m, 2 H); 8.21 (s, 2 H). 13C-NMR (100 MHz,
CDCl3): 56.07; 70.12 (2Â); 86.25; 93.65; 98.91; 101.65; 103.54; 106.32; 110.60; 117.11; 124.49; 124.58; 125.55;
125.86; 126.56; 127.27; 127.54; 127.99; 128.57; 130.31; 133.81; 134.31; 136.74; 139.00; 153.07; 159.65; 160.19.
‡
MALDI-TOF-MS (HABA): 1871 ([M ‡ Na] ). Anal. calc. for C124H102O16 ´ 2H2O (1884.2): C 79.05, H 5.67;
found: C 79.13, H 5.82.
(‡)-(S)-3,3'-Bis(2-{3,5-bis[3,5-bis(benzyloxy)benzyloxy]phenyl}-ethynyl)-1,1'-binaphthalene-2,2'-diol (G-
2-(‡)-(S)-20). To G-2-(‡)-(S)-19 (0.60 g, 0.33 mmol) in THF/MeOH 1 :1 (260 ml), conc. HCl (37%, 350 ml)
was added, and the soln. was stirred under N2 at 208 for 12 h. After addition of H2O (200 ml), the aq. phase was
extracted with CH2Cl2 (2 Â 200 ml), and the combined org. phases were dried (Na2SO4) and concentrated to
1
give crude G-2-(‡)-(S)-20 (0.58 g, 100%). Highly viscous oil. H-NMR (200 MHz, CDCl3): 5.00 (s, 8 H); 5.05
(s, 16 H); 5.19 (s, 2 H); 6.61 (t, J ˆ 2.0, 4 H); 6.66 (t, J ˆ 2.0, 2 H); 6.71 (d, J ˆ 2.0, 8 H); 6.85 (d, J ˆ 2.0, 4 H);
7.20 ± 7.46 (m, 46 H); 7.83 ± 7.87 (m, 2 H); 8.21 (s, 2 H).
Tetrabutylammonium
(‡)-(S)-3,3'-Bis(2-{3,5-bis[3,5-bis(benzyloxy)benzyloxy]phenyl}ethynyl)-1,1'-bi-
naphthalene-2,2'-diyl Phosphate (G-2-(‡)-(S)-2). To G-2-(‡)-(S)-20 (0.59 g, 0.33 mmol) in dry CH2Cl2
(66 ml), POCl3 (0.16m soln. in CH2Cl2, 6.6 ml, 0.72 mmol) and Et3N (0.94 g, 1.3 ml, 9.33 mmol) were added
at 208 under N2, and the soln. was stirred for 3 h. Evaporation in vacuo and addition of THF/H2O 1:1 (70 ml)
gave a mixture, which was stirred for 12 h at 408. CH2Cl2 (200 ml) and H2O (200 ml) were added, and the
separated org. phase was washed with H2O (2 Â 100 ml), dried (Na2SO4), and concentrated. CC (SiO2; CH2Cl2,
‡
containing 1.5% Et3N), followed by ion-exchange chromatography (Dowex 50WX8, Bu4N ; CH2Cl2/MeCN
1:1), afforded G-2-(‡)-(S)-2 (0.37 g, 54% from G-2-(‡)-(S)-19). Yellow foam. M.p. 688 (dec.). [a]rD:t: ˆ ‡101.8
(c ˆ 0.5, CHCl3). IR (KBr): 3022w, 2867w, 2200w, 1594s, 1506s, 1450m, 1242m, 1156s, 1061m, 969m, 828m.
1H-NMR (300 MHz, CDCl3): 0.76 ± 0.80 (m, 12 H); 1.13 ± 1.34 (m, 16 H); 2.94 (m, 8 H); 4.99 (s, 8 H); 5.03 (s,
16 H); 6.55 ± 6.58 (m, 6 H); 6.69 (d, J ˆ 2.1, 8 H); 6.92 (d, J ˆ 2.1, 4 H); 7.19 ± 7.43 (m, 46 H); 7.81 ± 7.84 (m, 2 H);
8.16 (s, 2 H). 13C-NMR (75 MHz, CDCl3): 13.67; 19.61; 23.82; 58.46; 70.17; 70.31; 87.25; 93.17; 101.81; 103.22;
106.63; 111.31; 118.04; 122.99; 123.02; 125.06; 125.87; 126.68; 127.08; 127.83; 128.26; 128.83; 130.35; 132.86;
133.97; 137.08; 139.52; 150.20 (d, J(31P, 13C) ˆ 9.8); 159.83; 160.50. 31P-NMR (121 MHz, CDCl3): 4.82. MALDI-
‡
TOF-MS (HABA): 1821 (100, [M À Bu4N] ). Anal. calc. for C136H128NO16P ´ 2H2O (2099.5): C 77.80, H 6.34,
N 0.67; found: C 77.74, H 6.60, N 0.92.

1368
Helvetica Chimica Acta ± Vol. 83 (2000)
(‡)-(S)-3,3'-Bis[2-(3,5-bis{3,5-bis[3,5-bis(benzyloxy)benzyloxy]benzyloxy}phenyl)ethynyl]-2,2'-bis(meth-
oxymethoxy)-1,1'-binaphthalene (G-3-(‡)-(S)-21). A soln. of (S)-13 (67 mg, 0.16 mmol) in abs. THF (1 ml) and
dry (i-Pr)2NH (2 ml) was slowly added (30 min) to a degassed soln. of G-3-10 (560 mg, 0.33 mmol),
[PdCl2(dppf)] (4.9 mg, 4 mol-%), and CuI (1.2 mg, 4 mol-%) in dry THF (2.5 ml) and dry (i-Pr)2NH (4 ml) at
408, and the mixture was stirred at 408 for 2 h. Sat. aq. NaCl soln. (20 ml) and CH2Cl2 (40 ml) were added, the
phases were separated, and the aq. phase was extracted with CH2Cl2 (2 Â 40 ml). The combined org. phases were
dried (Na2SO4), filtered through SiO2 and Celite, and concentrated. GPC (Bio-Beads SX-1) gave G-3-(‡)-(S)-
21 (320 mg, 57%). Highly viscous oil. [a]rD:t: ˆ ‡25.8 (c ˆ 0.5, CHCl3). IR (KBr): 3060w, 3024w, 2933m, 2869m,
1596s, 1492w, 1446m, 1369m, 1346w, 1319w, 1292w, 1269w, 1246w, 1214w, 1156s, 1050s, 978m. 1H-NMR
(300 MHz, CDCl3): 2.55 (s, 6 H); 4.95 ± 4.99 (m, 26 H); 5.03 (s, 32 H); 5.21 (d, AB, J ˆ 6.3, 2 H); 6.55 ± 6.62 (m,
20 H); 6.67 (t, J ˆ 2.1, 2 H); 6.71 (d, J ˆ 2.4, 16 H); 6.86 (d, J ˆ 2.1, 4 H); 7.27 ± 7.47 (m, 86 H); 7.64 (d, J ˆ 8.4,
2 H); 8.25 (s, 2 H). 13C-NMR (75 MHz, CDCl3): 56.24; 70.18; 70.26; 86.57; 93.90; 99.14; 101.89; 103.74; 106.65;
110.87; 117.37; 124.91; 125.85; 126.14; 126.86; 127.58; 127.84; 128.07; 128.26; 128.44; 128.59; 128.65; 128.86;
130.59; 134.12; 134.69; 137.10; 139.31; 139.52; 153.40; 160.07; 160.46; 160.52. MALDI-TOF-MS (HABA): 3586
‡
‡
(100, [M ‡ K] ), 3569 (88, [M ‡ Na] ). Anal. calc. for C236H198O32 ´ 2H2O (3582.21): C 79.13, H 5.68; found:
C 79.07, H 6.12.
(‡)-(S)-3,3'-Bis[2-(3,5-bis{3,5-bis[3,5-bis(benzyloxy)benzyloxy]benzyloxy}phenyl)ethynyl]-1,1'-binaphtha-
lene-2,2'-diol (G-3-(‡)-(S)-22). To G-3-(‡)-(S)-21 (300 mg, 0.09 mmol) in THF (40 ml), conc. HCl (37%,
75 ml) in MeOH (30 ml) was added, and the soln. was stirred under N2 at 208 for 24 h, then the reaction was
quenched with H2O (80 ml). The aq. phase was extracted with CH2Cl2 (2 Â 80 ml), and the combined org.
phases were dried (Na2SO4) and concentrated. CC (SiO2; CH2Cl2/Et3N 98 :2) provided G-3-(‡)-(S)-22 (264 mg,
85%). Highly viscous oil. [a]rD:t: ˆ ‡20.1 (c ˆ 0.5, CHCl3). IR (neat): 3500m (br.), 3062w, 3034w, 2922w, 2866w,
1
1596s, 1497m, 1451s, 1374m, 1343w, 1325w, 1292m, 1264m, 1157s, 1054s. H-NMR (300 MHz, CDCl3): 4.96 (s,
24 H); 5.01 (s, 32 H); 5.84 (s, 2 H); 6.54 ± 6.58 (m, 14 H); 6.66 (d, J ˆ 2.1, 8 H); 6.68 (d, J ˆ 2.4, 16 H); 6.83 (d, J ˆ
2.1, 4 H); 7.19 (d, J ˆ 8.4, 2 H); 7.27 ± 7.45 (m, 84 H); 7.83 (d, J ˆ 7.5, 2 H); 8.18 (s, 2 H). 13C-NMR (75 MHz,
CDCl3): 70.17; 70.25 (2Â); 84.05; 96.23; 101.89; 101.93; 104.14; 106.62; 110.95; 112.36; 113.67; 124.12; 124.65;
124.95; 127.83; 128.25; 128.42; 128.52; 128.57; 128.85; 129.06; 133.83; 134.05; 137.03; 139.23; 139.49; 151.22;
‡
160.05; 160.42; 160.49. MALDI-TOF-MS (HABA): 3482 ([M ‡ Na] ).
Tetrabutylammonium (‡)-(S)-3,3'-Bis[2-(3,5-bis{3,5-bis[3,5-bis(benzyloxy)benzyloxy]benzyloxy}phenyl)-
ethynyl]-1,1'-binaphthalene-2,2'-diyl Phosphate (G-3-(‡)-(S)-3). To a soln. of crude G-3-(‡)-(S)-22 (250 mg,
0.07 mmol) in dry CH2Cl2 (15 ml), POCl3 (0.2m soln. in CH2Cl2, 0.8 ml, 0.16 mmol) and Et3N (203 mg, 280 ml,
2.02 mmol) were added at 208 under N2, and the soln. was stirred for 3 h at 208. Evaporation in vacuo and
addition of THF/H2O 1:1 (16 ml) gave a mixture, which was stirred for 12 h at 308. CH2Cl2 (20 ml) and H2O
(20 ml) were added, and the separated org. phase was washed with H2O (2 Â 30 ml), dried (Na2SO4), and
concentrated. CC (SiO2, CH2Cl2/Et3N 98 :2), followed by ion-exchange chromatography (Dowex 50WX8,
‡
Bu4N ; CH2Cl2/MeCN 1 :1), afforded G-3-(‡)-(S)-3 (145 mg, 52%). Highly viscous oil. [a]rD:t: ˆ ‡63.7 (c ˆ 0.5,
CHCl3). IR (neat): 3059w, 3033w, 1595s, 1493w, 1450m, 1373m, 1343w, 1321w, 1291w, 1205w, 1156s, 1098w,
1050m, 972w. 1H-NMR (300 MHz, CDCl3): 0.77 (t, J ˆ 6.9, 12 H); 1.10 ± 1.21 (m, 8 H); 1.23 ± 1.38 (m, 8 H);
2.88 ± 2.98 (m, 8 H); 4.96 (s, 16 H); 4.97 (s, 8 H); 5.00 (s, 32 H); 6.53 ± 6.57 (m, 14 H); 6.60 (t, J ˆ 2.1, 8 H); 6.69
(d, J ˆ 1.8, 16 H); 6.83 (d, J ˆ 2.1, 4 H); 7.18 ± 7.40 (m, 86 H); 7.81 (d, J ˆ 8.1, 2 H); 8.15 (s, 2 H). 13C-NMR
(125 MHz, CDCl3): 13.64; 19.57; 23.76; 58.39; 70.01; 70.10 (2Â); 87.26; 92.90; 103.05; 106.42; 110.99; 117.62;
122.78; 124.69; 125.31; 125.72; 126.33; 126.91; 127.55; 127:71; 127.98; 128.24; 128.40; 128.57; 129.05; 130.14;
132.68; 133.76; 136.79; 139.24; 159.51; 160.06; 160.16 (2Â). 31P-NMR (202 MHz, CDCl3): 4.85. MALDI-TOF-
‡
‡
MS (HABA): 3562 (61, [M À Bu4N ‡ 2 Na] ), 3540 (100, [MH À Bu4N ‡ Na] ). Anal. calc. for C248H224NO32P ´
2H2O (3797.54): C 78.44, H 6.05; N 0.37; found: C 78.13, H 6.16, N 0.52.
(‡)-(S)-3,3'-Bis{2-[3,5-bis(3,5-bis{2-[2-(2-methoxyethoxy)ethoxy]ethoxy}benzyloxy)phenyl]ethynyl}-2,2'-
bis(methoxymethoxy)-1,1'-binaphthalene (G-1-(‡)-(S)-24). A degassed soln. of (S)-13 (50 mg, 0.12 mmol) in
abs. THF (2 ml) was added to a degassed soln. of [PdCl2(dppf)] (8.5 mg, 5 mol-%), CuI (1.1 mg, 5 mol-%), and
G-1-11 (0.30 g, 0.37 mmol) in dry (i-Pr)2NH (2.5 ml) and THF (3.5 ml), and the mixture was warmed to 408 for
12 h. Sat. aq. NaCl soln. (20 ml) and CH2Cl2 (30 ml) were added, the phases were separated, and the aq. phase
was extracted with CH2Cl2 (2 Â 30 ml). The combined org. phases were dried (Na2SO4), filtered through SiO2
and Celite, and concentrated. GPC (Biobeads SX-1) provided G-1-(‡)-(S)-24 (0.18 g, 65%). Highly viscous oil.
[a]rD:t: ˆ ‡64.4 (c ˆ 1.0, CHCl3). IR (KBr): 2920m, 2869s, 2817w, 1596s, 1449m, 1350m, 1321w, 1296w, 1240m,
1
1171s, 1147s, 1107s, 1068m, 978m, 844m. H-NMR (500 MHz, CDCl3): 2.55 (s, 6 H); 3.36 (s, 24 H); 3.52 ± 3.54
(m, 16 H); 3.63 ± 3.68 (m, 32 H); 3.71 ± 3.73 (m, 16 H); 3.83 (t, J ˆ 4.8, 16 H); 4.11 (t, J ˆ 4.8, 16 H); 4.94 (d, AB,
J ˆ 6.2, 2 H); 4.95 (s, 8 H); 5.17 (d, AB, J ˆ 6.2, 2 H); 6.45 (t, J ˆ 2.2, 4 H); 6.58 (d, J ˆ 2.2, 8 H); 6.59 (t, J ˆ 2.3,

Helvetica Chimica Acta ± Vol. 83 (2000)
1369
2 H); 6.72 (d, J ˆ 2.3, 4 H); 7.22 (t, J ˆ 7.9, 2 H); 7.28 ± 7.32 (m, 2 H); 7.41 ± 7.44 (m, 2 H); 7.86 (d, J ˆ 8.2, 2 H);
8.23 (s, 2 H). 13C-NMR (125 MHz, CDCl3): 56.05; 58.98; 67.47; 69.62; 70.03; 70.52; 70.61; 70.77; 71.89; 86.21;
93.59; 98.85; 101.17; 103.41; 106.03; 110.48; 117.08; 124.52; 125.51; 125.80; 126.51; 127.23; 127.54; 130.27; 133.77;
‡
134.33; 138.79; 152.98; 159.65; 160.09. MALDI-TOF-MS (2,5-DHB): 2321 (100, [MH ‡ Na] ), 2277 (53,
‡
[MH ‡ Na À CH2OMe] ). Anal. calc. for C124H166O40 ´ H2O (2314.64): C 64.21, H 7.32; found: C 64.21, H 7.45.
(‡)-(S)-3,3'-Bis{2-[3,5-bis(3,5-bis{2-[2-(2-methoxyethoxy)ethoxy]ethoxy}benzyloxy)phenyl]ethynyl}-1,1'-
binaphthalene-2,2'-diol (G-1-(‡)-(S)-25). To G-1-(‡)-(S)-24 (150 mg, 0.065 mmol) in THF/MeOH 1:1 (40 ml),
conc. HCl (37%, 60 ml) was added, and the soln. was stirred under N2 at 208 for 12 h. After addition of H2O
(60 ml), the aq. phase was extracted with CH2Cl2 (2 Â 80 ml), and the combined org. phases were dried
(Na2SO4) and concentrated to give crude G-1-(‡)-(S)-25. Highly viscous oil. 1H-NMR (300 MHz, CDCl3): 3.35
(s, 24 H); 3.52 ± 3.56 (m, 16 H); 3.62 ± 3.69 (m, 32 H); 3.71 ± 3.73 (m, 16 H); 3.81 (t, J ˆ 4.8, 16 H); 4.10 (t, J ˆ 4.8,
16 H); 4.96 (s, 8 H); 6.01 (s, 2 H); 6.44 (t, J ˆ 1.8, 4 H); 6.58 (d, J ˆ 1.8, 8 H); 6.61 (t, J ˆ 2.1, 2 H); 6.80 (d, J ˆ 2.1,
4 H); 7.17 (d, J ˆ 8.1, 2 H); 7.26 ± 7.39 (m, 4 H); 7.86 (d, J ˆ 8.1, 2 H); 8.20 (s, 2 H).
Tetrabutylammonium
(‡)-(S)-3,3'-Bis{2-[3,5-bis(3,5-bis{2-[2-(2-methoxyethoxy)ethoxy]ethoxy}benzyl-
oxy)phenyl]ethynyl}-1,1'-binaphthalene-2,2'-diyl Phosphate (G-1-(‡)-(S)-23). To G-1-(‡)-(S)-25 (145 mg,
0.065 mmol) in dry CH2Cl2 (12 ml), POCl3 (0.2m soln. in CH2Cl2, 0.7 ml, 0.14 mmol) and Et3N (0.18 g,
0.26 ml, 1.85 mmol) were added at 208 under N2, and the soln. was stirred for 3 h. After evaporation in vacuo,
THF/H2O 1:1 (20 ml) was added, and the mixture was stirred for 12 h at 408. CH2Cl2 (50 ml) and H2O (50 ml)
were added, and the separated org. phase was washed with H2O (2 Â 50 ml), dried (Na2SO4), and concentrated.
‡
CC (CH2Cl2/AcOEt/Et3N 50 :47:3), followed by ion-exchange chromatography (Dowex 50WX8, Bu4N ;
CH2Cl2/MeCN 1:1), afforded G-1-(‡)-(S)-23 (100 mg, 61%). Yellow foam. [a]rD:t: ˆ ‡169.2 (c ˆ 1.0, CDCl3). IR
(KBr): 3070w, 2932s, 2874s, 2220w, 1597s, 1448s, 1351m, 1324w, 1297m, 1251m, 1168s, 1139s, 1109s, 1060m, 953w,
847m. 1H-NMR (500 MHz, CDCl3): 1.17 ± 1.25 (m, 12 H); 1.34 ± 1.39 (m, 8 H); 1.92 ± 2.16 (m, 8 H); 3.00 ± 3.34
(m, 8 H); 3.36 (s, 24 H); 3.52 ± 3.54 (m, 16 H); 3.62 ± 3.67 (m, 32 H); 3.70 ± 3.72 (m, 16 H); 3.82 (t, J ˆ 4.8, 16 H);
4.10 (t, J ˆ 4.8, 16 H); 4.95 (s, 8 H); 6.44 (t, J ˆ 2.2, 4 H); 6.56 (t, J ˆ 2.3, 2 H); 6.58 (d, J ˆ 2.2, 8 H); 6.89 (d, J ˆ
2.3, 4 H); 7.17 ± 7.24 (m, 4 H); 7.35 (m, 2 H); 7.82 (d, J ˆ 8.4, 2 H); 8.16 (s, 2 H). 13C-NMR (125 MHz, CDCl3):
13.60; 19.56; 23.78; 58.47; 58.97; 67.49; 69.62; 70.02; 70.51; 70.60; 70.74; 71.89; 87.13; 92.73; 101.20; 102.99;
106.06; 110.91; 117.61; 122.74; 124.65; 125.64; 126.28; 126.86; 127.86; 130.09; 132.64; 133.78; 138.96; 149.82 (d,
J(31P, 13C) ˆ 9.4); 159.47; 160.05. 31P-NMR (121 MHz, CDCl3): 4.79. MALDI-TOF-MS (HABA): 2316 (100,
‡
‡
[MH À Bu4N ‡ 2 Na] ), 2294 (17, [MH2 À Bu4N ‡ Na] ).
1-[3,5-Bis(benzyloxy)phenyl]-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (28). To a soln. of G-1-8 (1.00 g,
1.18 mmol) in dioxane (10 ml), [PdCl2(dppf)] (29 mg, 3 mol-%), Et3N (0.36 mg, 0.49 ml, 3.56 mmol), and
(pinacolato)boron (0.23 g, 0.25 ml, 1.78 mmol) were added, and the mixture was heated to 808 for 12 h. H2O
(30 ml), and CH2Cl2 (30 ml) were added, and, after filtration over Celite, the phases were separated. The aq.
phase was extracted with CH2Cl2 (40 ml), the combined org. phases were dried (Na2SO4), and the solvent was
evaporated in vacuo. CC (SiO2; hexane/AcOEt 10 :1, containing 0.5% Et3N) provided 28 (540 mg, 54%). White
solid. M.p. 1288. IR (KBr): 3068w, 3034w, 2975m, 2866m, 1587s, 1495w, 1474m, 1460m, 1430m, 1345s, 1359s,
1311m, 1276w, 1217m, 1159s, 1104w, 1053m, 1025m, 968m. 1H-NMR (300 MHz, CDCl3): 1.38 (s, 12 H); 5.08
(s, 4 H); 6.57 (t, J ˆ 2.1, 1 H); 7.12 (d, J ˆ 2.1, 2 H); 7.33 ± 7.49 (m, 10 H). 13C-NMR (75 MHz, CDCl3): 24.86;
70.07; 83.91; 105.84; 113.01; 127.54; 127.87; 128.51; 137.07; 159.66 (signal for the C-atom next to B-atom not
‡
‡
visible). FAB-MS: 416 (100, M ). HR-EI-MS: 416.2156 (M , C26H29BO4; calc. 416.2159).
(‡)-(S)-3,3'-Bis[3,5-bis(benzyloxy)phenyl]-2,2'-bis(methoxymethoxy)-1,1'-binaphthalene
(G-1-(‡)-(S)-
29). To a degassed soln. of (‡)-(S)-27 (290 mg, 0.46 mmol), 28 (400 mg, 0.96 mmol), and Na2CO3 (195 mg,
1.84 mmol) in H2O (6.5 ml) and DME (14 ml), [PdCl2(PPh3)2] (45 mg, 8 mol-%) was added, and the mixture
was warmed to 858 for 3 h. Sat. aq. NaCl soln. (20 ml) and CH2Cl2 (30 ml) were added, the phases were
separated, and the aq. phase was extracted with CH2Cl2 (30 ml). The combined org. phases were dried (Na2SO4)
and concentrated. CC (SiO2; hexane/AcOEt 5:1, containing 0.5% Et3N) afforded G-1-(‡)-(S)-29 (350 mg,
80%). White foam. M.p. 718. [a]rD:t: ˆ ‡24.5 (c ˆ 0.5, CHCl3). IR (neat): 3059m, 3023m, 2924m, 2825w, 1593s,
1493m, 1452m, 1416m, 1371m, 1344m, 1267m, 1231w, 1120w, 1155s, 1082m, 1057m, 1028m, 970m, 916m.
1H-NMR (500 MHz, CDCl3): 2.33 (s, 6 H); 4.37 (d, AB, J ˆ 5.9, 2 H); 4.39 (d, AB, J ˆ 5.9, 2 H); 5.11 (s, 8 H);
6.67 (t, J ˆ 2.3, 2 H); 7.02 (d, J ˆ 2.3, 4 H); 7.28 ± 7.47 (m, 26 H); 7.87 (d, J ˆ 8.1, 2 H); 7.93 (s, 2 H). 13C-NMR
(75 MHz, CDCl3): 55.77; 70.22; 98.41; 101.28; 109.07; 125.12; 126.30; 126.47; 126.54; 127.62; 127.83; 127.96;
‡
128.57; 130.41; 130.69; 133.64; 135.03; 136.94; 141.09; 151.29; 159.78. FAB-MS: 951 (4, M ), 887 (100). Anal.
calc. for C64H54O8 ´ 1.5H2O (978.16): C 78.59, H 5.87; found: C 78.88, H 6.03.
(‡)-(S)-3,3'-Bis[3,5-bis(benzyloxy)phenyl]-1,1'-binaphthalene-2,2'-diol (G-1-(‡)-(S)-30). To G-1-(‡)-(S)-
29 (350 mg, 0.37 mmol) in THF (100 ml), conc. HCl (37%, 350 ml) in MeOH (100 ml) was added, and the soln.

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Helvetica Chimica Acta ± Vol. 83 (2000)
was stirred for 20 h under N2 at 208. H2O (100 ml) and CH2Cl2 (150 ml) were added, the aq. phase was extracted
with CH2Cl2 (100 ml), and the combined org. phases were dried (Na2SO4) and concentrated. CC (SiO2; hexane/
AcOEt 5 :1, containing 0.5% Et3N) gave G-1-(‡)-(S)-30 (180 mg, 57%). Viscous oil. 1H-NMR (200 MHz,
CDCl3): 5.11 (s, 8 H); 5.44 (s, 2 H); 6.70 (t, J ˆ 2.4, 2 H); 7.00 (d, J ˆ 2.4, 4 H); 7.25 ± 7.49 (m, 26 H); 7.92 (d, J ˆ
8.0, 2 H); 8.02 (s, 2 H).
Tetrabutylammonium (‡)-(S)-3,3'-Bis[3,5-bis(benzyloxy)phenyl]-1,1'-binaphthalene-2,2'-diyl Phosphate
(G-1-(‡)-(S)-26). To G-1-(‡)-(S)-30 (85 mg, 0.10 mmol) in dry CH2Cl2 (20 ml), POCl3 (0.2m soln. in CH2Cl2;
2.2 ml, 0.22 mmol) and Et3N (0.28 g, 0.39 ml, 2.8 mmol) were added at 208 under N2, and the soln. was stirred for
4 h. After evaporation in vacuo, THF/H2O 1:1 (20 ml) was added, and the mixture was stirred for 12 h
at 308. CH2Cl2 (30 ml) and H2O (20 ml) were added, and the separated org. phase was washed with H2O
(30 ml), dried (Na2SO4), and concentrated. CC (SiO2; CH2Cl2/Et3N 98 :3), followed by ion-exchange
‡
chromatography (Dowex 50WX8, Bu4N ; CH2Cl2/MeCN 1 :1), afforded G-1-(‡)-(S)-26 (110 mg, 93%). M.p.
1
1128. [a]rD:t: ˆ ‡80.7 (c ˆ 0.5, CHCl3). H-NMR (500 MHz, CDCl3): 0.71 (t, J ˆ 7.3, 12 H); 1.03 ± 1.05 (m, 8 H);
1.11 ± 1.18 (m, 8 H); 2.69 ± 2.73 (m, 8 H); 5.13 (d, AB, J ˆ 11.7, 4 H); 5.18 (d, AB, J ˆ 11.7, 4 H); 6.64 (t, J ˆ 2.2,
2 H); 7.15 ± 7.18 (m, 4 H); 7.34 ± 7.37 (m, 14 H); 7.46 ± 7.48 (m, 12 H); 7.86 (d, J ˆ 8.2, 2 H); 7.93 (s, 2 H).
13C-NMR (125 MHz, CDCl3): 13.53; 19.40; 23.61; 58.08; 70.18; 101.48; 109.78; 123.48; 124.37; 125.45; 126.97;
127.67; 127.73; 128.06; 128.37; 130.22; 130.51; 132.64; 135.07; 137.43; 141.00; 147.98 (d, J(31P, 13C) ˆ 9.4); 159.31.
‡
‡
31P-NMR (121 MHz, CDCl3): 4.86. FAB-MS: 1408 (10, [MH ‡ Bu4N] ), 1166 (11, MH ), 925 (23, [MH À
‡
‡
Bu4N] ), 242 (100, Bu4N ). Anal. calc. for C76H80NO8P ´ 2H2O (1202.49): C 75.91, H 7.04, N 1.16; found:
C 75.98, H 7.22, N 1.23.
(‡)-(S,S)-3,3'-(Buta-1,3-diynediyl)bis(3'-ethynyl-1,1'-binaphthalene-2,2'-diol) ((‡)-(S,S)-34). To (S,S)-33
(80 mg, 0.11 mmol) in THF (100 ml), conc. HCl (37%, 300 ml) in MeOH (100 ml) was added, and the soln. was
stirred for 10 h under N2 at 208. H2O (200 ml) and CH2Cl2 (160 ml) were added, the aq. phase was extracted with
CH2Cl2 (2 Â 120 ml), and the combined org. phases were dried (Na2SO4) and evaporated in vacuo to give crude
1
(‡)-(S)-34 (74 mg, 98%). Highly viscous oil. H-NMR (300 MHz, CDCl3): 3.26 (s, 2 H); 5.63 (s, 2 H); 5.79 (s,
2 H); 7.08 ± 7.14 (m, 4 H); 7.26 ± 7.40 (m, 8 H); 7.83 ± 7.86 (m, 4 H); 8.19 (s, 2 H); 8.23 (s, 2 H).
Bis(tetrabutylammonium)
(‡)-(S,S)-3,3'-(Buta-1,3-diynediyl)bis(3'-ethynyl-1,1'-binaphthalene-2,2'-diyl
Phosphate) ((‡)-(S,S)-31). To (S,S)-34 (70 mg, 0.10 mmol) in dry CH2Cl2 (30 ml), POCl3 (0.2m soln. in
CH2Cl2, 2.2 ml, 0.44 mmol) and Et3N (0.60 g, 0.82 ml, 6.0 mmol) were added at 208 under N2, and the soln. was
stirred for 3 h. After evaporation, THF (10 ml) and H2O (10 ml) were added, and the mixture was stirred for
12 h at 308. Evaporation in vacuo, addition of CH2Cl2 (25 ml) and H2O (20 ml), and phase separation provided
an org. phase, which was washed with H2O (3 Â 20 ml), dried over Na2SO4, and evaporated in vacuo. CC (SiO2;
CH2Cl2/Et3N 97:3 ! 95 :5), followed by dissolving the product in CH2Cl2 (15 ml), washing with H2O (10 ml),
‡
and ion-exchange chromatography (Dowex 50WX8, Bu4N ; CH2Cl2/MeCN 1:1), provided (‡)-(S,S)-31 (68 mg,
53%). Yellow foam. M.p. > 2508. [a]rD:t: ˆ ‡247.3 (c ˆ 0.5, CHCl3). IR (KBr): 3422s, 2961m, 2922w, 2867w,
1617w, 1483w, 1451w, 1417m, 1306m, 1283m, 1250w, 1200w, 1150w, 1111s, 1097s, 1017w, 961w, 906w, 811w.
1H-NMR (500 MHz, CDCl3): 0.78 (t, J ˆ 7.3, 24 H); 1.16 ± 1.25 (m, 16 H); 1.41 ± 1.47 (m, 16 H); 2.99 ± 3.12 (m,
16 H); 3.28 (s, 2 H); 7.19 ± 7.22 (m, 4 H); 7.30 ± 7.38 (m, 8 H); 7.80 (d, J ˆ 8.2, 2 H); 7.81 (d, J ˆ 8.2, 2 H); 8.12 (s,
2 H); 8.16 (s, 2 H). 13C-NMR (125 MHz, CDCl3): 13.65; 19.56; 23.82; 58.48; 78.29; 79.95; 80.21; 81.51; 116.58;
117.06; 122.26; 123.07; 124.83; 125.09; 126.53; 126.59; 126.96; 127.02; 127.92; 128.04; 129.97 (2Â); 132.51; 132.96;
134.53; 135.36; 150.26; 150.33. 31P-NMR (121 MHz, CDCl3): 4.76. FAB-MS: 1516 (10, [M ‡ Bu4N] ), 1275 (12,
‡
‡
‡
MH ), 242 (100, Bu4N ). Anal. calc. for C80H94N2O8P2 ´ H2O (1291.61): C 74.39, H 7.49, N 2.17; found: C 74.10,
H 7.58, N 2.26.
(‡)-(S)-2,2'-Bis(methoxymethoxy)-3-iodo-3'-[2-(trimethylsilyl)ethynyl]-1,1'-binaphthalene ((‡)-(S)-35).
To a degassed soln. of (‡)-(S)-27 (2.50 g, 3.99 mmol) in Et3N (40 ml) and abs. toluene (40 ml), [PdCl2(PPh3)2]
(79 mg, 5 mol-%), CuI (38 mg, 5 mol-%), and (trimethylsilyl)acetylene (0.79 g, 1.13 ml, 7.98 mmol) were added,
and the mixture was heated to 408 for 4 h. Sat. aq. NaCl soln. (300 ml) and CH2Cl2 (250 ml) were added, the
phases were separated, and the aq. phase was extracted with CH2Cl2 (2 Â 250 ml). The combined org. phases
were washed with sat. aq. NaHCO3 soln., dried (Na2SO4), and evaporated in vacuo. CC (hexane/CH2Cl2 1:1,
containing 0.5% Et3N) provided (‡)-(S)-35 (0.70 g, 30%) besides dialkynylated product (0.43 g, 19%) and
starting material (‡)-(S)-27 (0.59 g, 24%). M.p. 658. [a]rD:t: ˆ ‡13.3 (c ˆ 1.0, CHCl3). IR (KBr): 3051w, 2997w,
2954m, 2900w, 2825w, 2145w, 1490w, 1447w, 1426w, 1383m, 1350m, 1245m, 1194w, 1159s, 1102w, 1081w, 1054m,
1026w, 979s, 930s, 908m, 876m, 844s, 779w, 751m, 714w. 1H-NMR (200 MHz, CDCl3): 0.27 (s, 9 H); 2.44 (s, 3 H);
2.63 (s, 3 H); 4.75 (d, AB, J ˆ 5.6, 1 H); 4.78 (d, AB, J ˆ 5.6, 1 H); 4.93 (d, AB, J ˆ 6.2, 1 H); 5.14 (d, AB, J ˆ 6.2,
1 H); 7.18 (d, J ˆ 8.4, 2 H); 7.26 ± 7.32 (m, 4 H); 7.39 ± 7.44 (m, 2 H); 8.18 (s, 1 H); 8.53 (s, 1 H). 13C-NMR
(75 MHz, CDCl3): À0.13; 55.98; 56.76; 92.59; 98.85; 99.55; 99.63; 101.91; 117.28; 125.82; 126.00 (2Â); 126.43;

Helvetica Chimica Acta ± Vol. 83 (2000)
1371
126.63; 126.86; 126.94; 127.11; 127.76; 127.89; 130.33; 132.53; 134.02; 134.18; 135.41; 140.04; 152.40; 153.69. FAB-
‡
‡
‡
MS: 596 (13, M ), 565 (30, [M À OCH3] ), 521 (100, [M À C4H11O] ). Anal. calc. for C29H29IO4Si (596.54):
C 58.39, H 4.90; found: C 58.02, H 4.96.
(‡)-(S)-2,2'-Bis(methoxymethoxy)-3-iodo-3'-[2-(triisopropylsilyl)ethynyl]-1,1'-binaphthalene ((‡)-(S)-36).
To
a
degassed soln. of (‡)-(S)-27 (1.50 g, 2.40 mmol) in Et3N (24 ml) and abs. toluene (24 ml),
[PdCl2(PPh3)2Cl2] (47 mg, 5 mol-%), CuI (23 mg, 0.12 mmol, 5 mol-%), and (triisopropylsilyl)acetylene
(0.87 g, 1.06 ml, 4.791 mmol) were added, and the mixture was heated to 408 for 3 h. Sat. aq. NaCl soln. (50 ml)
and CH2Cl2 (100 ml) were added, the phases were separated, and the aq. phase was extracted with CH2Cl2 (2 Â
100 ml). The combined org. phases were washed with sat. aq. NaHCO3 soln., dried (Na2SO4), and evaporated in
vacuo. CC (hexane/CH2Cl2 5 :1, containing 0.5% Et3N) yielded (‡)-(S)-36 (0.49 g, 30%), in addition to
dialkynylated material (0.65 g, 37%). M.p. 538. [a]rD:t: ˆ ‡1.0 (c ˆ 1.0, CHCl3). IR (KBr): 3048w, 2941m, 2850m,
2146m, 1616w, 1589w, 1561w, 1490w, 1462m, 1446m, 1424m, 1385m, 1347m, 1242m, 1204m, 1160s, 1099w, 1077m,
1055s, 979s, 929s, 885s, 808w, 780w, 749s. 1H-NMR (500 MHz, CDCl3): 1.20 (ms, 21 H); 2.33 (s, 3 H); 2.72 (s,
3 H); 4.78 (d, AB, J ˆ 5.5, 1 H); 4.83 (d, AB, J ˆ 5.5, 1 H); 5.03 (d, AB, J ˆ 6.3, 1 H); 5.32 (d, AB, J ˆ 6.3, 1 H);
7.18 ± 7.23 (m, 2 H); 7.28 ± 7.31 (m, 2 H); 7.41 ± 7.44 (m, 2 H); 7.78 (d, J ˆ 8.2, 1 H); 7.85 (d, J ˆ 8.2, 1 H); 8.22 (s,
1 H); 8.55 (s, 1 H). 13C-NMR (125 MHz, CDCl3): 11.32; 18.66; 55.53; 56.58; 92.39; 95.89; 98.58; 99.18; 103.49;
117.18; 125.44; 125.64; 125.69; 126.20; 126.28; 126.45; 126.66; 126.73; 127.36; 127.43; 129.98; 132.17; 133.61;
‡
‡
133.95; 135.61; 139.57; 151.88; 153.16. FAB-MS: 681 (7, M ), 461 (100, [M À (i-Pr)3Si À 2 MeO] ). Anal. calc.
for C35H41IO4Si (680.70): C 61.76, H 6.07; found: C 61.61, H 5.88.
Dialkynylated Side-Product (À)-(S)-2,2'-Bis(methoxymethoxy)-3,3'-bis[2-(triisopropylsilyl)ethynyl]-1,1'-
binaphthalene. M.p. 1338. [a]rD:t: ˆ À0.4 (c ˆ 1.0, CHCl3). IR (KBr): 3051w, 2942s, 2864s, 2151m, 1622w, 1583w,
1491w, 1463m, 1426m, 1391m, 1352w, 1322w, 1287w, 1243m, 1202w, 1159s, 1099w, 1071m, 1017w, 977s, 915m,
883m, 786w, 750m. 1H-NMR (500 MHz, CDCl3): 1.16 (ms, 42 H); 2.34 (s, 6 H); 4.95 (d, AB, J ˆ 6.2, 2 H); 5.34 (d,
AB, J ˆ 6.2, 2 H); 7.15 (d, J ˆ 8.33, 2 H); 7.24 ± 7.27 (m, 2 H); 7.38 ± 7.41 (m, 2 H); 7.81 (d, J ˆ 8.2, 2 H); 8.16 (s,
2 H). 13C-NMR (125 MHz, CDCl3): 11.41; 18.72; 55.76; 95.69; 98.60; 103.77; 117.19; 125.38; 125.97; 126.70;
‡
‡
127.01; 127.27; 130.12; 133.94; 135.40; 153.01. FAB-MS: 735 (17, M ); 515 (100, [M À (i-Pr)3Si À 2 MeO] ).
Anal. calc. for C46H62O4Si2 (735.2): C 75.15, H 8.50; found: C 75.21, H 8.44.
2,2'-(1,4-Phenylene)bis(4,4,5,5-tetramethyl-1,3,2-dioxoborolane) (37). To 1,4-diiodobenzene (1.00 g,
3.0 mmol) in dioxane (24 ml) and Et3N (0.92 g, 1.3 ml, 9.1 mmol), [PdCl2(dppf)] (74 mg, 3 mol-%) and
(pinacolato)boron (1.16 g, 1.3 ml, 9.1 mmol) were added, and the mixture was heated to 808 for 12 h. After
cooling, H2O (20 ml) was added, and the mixture was extracted with CH2Cl2 (3 Â 30 ml). The combined org.
phases were washed with sat. aq. NaHCO3 soln., dried (Na2SO4), and evaporated in vacuo. Recrystallization
(hexane) yielded 37 (443 mg, 44%). Brown needles. M.p. 2408 ([44]: 243 ± 2458). IR (KBr): 2978m, 2942w,
1522m, 1463w, 1393m, 1352s, 1322m, 1273w, 1256w, 1213w, 1169w, 1142s, 1102s, 1120m, 962w, 857m, 826w, 799w,
669m. 1H-NMR (300 MHz, CDCl3): 1.35 (s, 24 H); 7.80 (s, 4 H). 13C-NMR (75 MHz, CDCl3): 24.92; 84.02;
‡
‡
134.15 (signal for the C-atom next to B-atom not visible). FAB-MS: 330 (28, M ), 231 (100, [M À C6H11O] ).
Anal. calc. for C18H28B2O4 (330.04): C 65.51, H 8.55; found: C 65.39, H 8.62.
(‡)-(S,S)-3,3'-(1,4-Phenylene)bis{2,2'-bis(methoxymethoxy)-3'-[2-(triisopropylsilyl)ethynyl]-1,1'-binaphtha-
lene} ((‡)-(S,S)-38). To (‡)-(S)-36 (200 mg, 0.30 mmol) and 37 (48 mg, 0.15 mmol) in benzene (6.5 ml) and
EtOH (1.8 ml), a soln. of Na2CO3 (62 mg, 0.59 mmol) in H2O (5 ml) and [PdCl2(dppf)] (4.8 mg, 4 mol-%) were
added, and the vigorously stirred mixture was heated to 808 under Ar for 4 h. A second portion of [PdCl2(dppf)]
(4.8 mg, 4 mol-%) was added, and stirring was continued for another 4 h at 808. After a third addition of
[PdCl2(dppf)] (2.4 mg, 2 mol-%) and heating for 4 h, the mixture was cooled to 208 and evaporated in vacuo.
The residue was extracted with CH2Cl2 (3 Â 20 ml), and the combined org. phases were washed with sat. aq.
NaHCO3 and NaCl solns., dried (Na2SO4), and concentrated. GPC (Bio-Beads SX-3) afforded (‡)-(S,S)-38
(130 mg, 74%). M.p. 1128. [a]rD:t: ˆ ‡124.8 (c ˆ 1.0, CHCl3). IR (KBr): 3056w, 2941s, 2853s, 2360m, 2137w, 1615w,
1588w, 1562w, 1540w, 1492w, 1460m, 1444m, 1423m, 1389m, 1353m, 1327w, 1241m, 1199m, 1159s, 1097m, 1078m,
1
1054m, 1022w, 988s, 965s, 942m, 916m, 884m, 841w, 814w, 782w, 749m. H-NMR (200 MHz, CDCl3): 1.19 (ms,
42 H); 2.30 (s, 6 H); 2.44 (s, 6 H); 4.40 (d, AB, J ˆ 6.2, 2 H); 4.45 (d, AB, J ˆ 6.2, 2 H); 5.06 (d, AB, J ˆ 6.2, 2 H);
5.33 (d, AB, J ˆ 6.2, 2 H); 7.20 ± 7.31 (m, 8 H); 7.38 ± 7.49 (m, 4 H); 7.84 (d, J ˆ 8.2, 2 H); 7.89 (s, 4 H); 7.92 (d, J ˆ
8.2, 2 H); 8.03 (s, 2 H); 8.19 (s, 2 H). 13C-NMR (125 MHz, CDCl3): 11.47; 18.80; 55.79; 56.04; 95.91; 98.75; 98.92;
104.09; 117.67; 125.53; 125.66; 126.42; 126.53; 126.81 (2Â); 127.00; 127.37; 127.68; 128.00; 129.85; 130.46; 130.96;
131.11; 133.92; 134.25; 135.09; 135.69; 138.36; 151.61; 153.42. MALDI-TOF-MS (HABA): 1223 (13, [MH ‡
‡
‡
‡
‡
K] ), 1208 (61, [MH2 ‡ Na] ), 1207 (100, [MH ‡ Na] ), 1206 (98, [M ‡ Na] ).
(‡)-(S,S)-3,3'-(1,4-Phenylene)bis[2,2'-bis(methoxymethoxy)-3'-ethynyl-1,1'-binaphthalene] ((‡)-(S,S)-39).
A soln. of (‡)-(S,S)-38 (130 mg, 0.13 mmol) and Bu4NF (519 ml, 1.0m soln. in THF, 0.512 mmol) in THF (13 ml)

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Helvetica Chimica Acta ± Vol. 83 (2000)
was stirred for 1 h at 208 under N2. After addition of H2O (30 ml), the mixture was extracted with CH2Cl2 (3 Â
30 ml), and the combined org. phases were dried (Na2SO4). Evaporation in vacuo and CC (SiO2; hexane/
AcOEt 3 :1, containing 0.5% Et3N) provided (S,S)-39 (115 mg, 97%). White powder. M.p. 688. [a]rD:t: ˆ ‡123.2
(c ˆ 1.0, CHCl3). IR (KBr): 3059w, 2945m, 2856m, 2106w, 2071w, 1617w, 1591m, 1490m, 1464s, 1424s, 1389s,
1354s, 1241s, 1201m, 1159s, 1096m, 1075m, 1044m, 986s, 974s, 934m, 912m, 881w, 838w. 1H-NMR (300 MHz,
CDCl3): 2.23 (s, 6 H); 2.66 (s, 6 H); 3.35 (s, 2 H); 4.35 (d, AB, J ˆ 6.3, 2 H); 4.40 (d, AB, J ˆ 6.3, 2 H); 4.98 (d, AB,
J ˆ 6.0, 2 H); 5.07 (d, AB, J ˆ 6.0, 2 H); 7.21 (d, J ˆ 8.1, 4 H); 7.26 ± 7.32 (m, 4 H); 7.40 ± 7.46 (m, 4 H); 7.83 ± 7.93
(m, 8 H); 8.02 (s, 2 H); 8.21 (s, 2 H). 13C-NMR (75 MHz, CDCl3): 55.80; 56.16; 80.72; 81.53; 98.57; 98.97; 116.37;
125.32; 125.56; 125.79; 126.30; 126.50; 126.68; 126.72; 127.38; 127.58; 127.89; 129.58; 130.19; 130.86; 130.87;
‡
133.46; 134.20; 134.80; 135.06; 138.02; 151.45; 153.27. MALDI-TOF-MS (2,5-DHB): 893 ([M ‡ Na] ).
(‡)-(S,S)-3,3'-(1,4-Phenylene)bis(3'-ethynyl-1,1'-binaphthalene-2,2'-diol) ((‡)-(S,S)-40). To (‡)-(S,S)-39
(35 mg, 0.046 mmol) in THF (50 ml), conc. HCl (37%, 150 ml) in MeOH (50 ml) was added, and the soln. was
stirred for 10 h under N2 at 208. H2O (100 ml) and CH2Cl2 (80 ml) were added, the aq. phase was extracted with
CH2Cl2 (2 Â 60 ml), and the combined org. phases were dried (Na2SO4) and evaporated in vacuo to give crude
(‡)-(S,S)-40. Highly viscous oil. 1H-NMR (300 MHz, CDCl3): 3.26 (s, 2 H); 5.28 (s, 2 H); 5.81 (s, 2 H); 7.13 (d,
J ˆ 7.8, 4 H); 7.26 ± 7.42 (m, 8 H); 7.83 ± 7.93 (m, 8 H); 8.02 (s, 2 H); 8.21 (s, 2 H).
Bis(tetrabutylammonium) (‡)-(S,S)-3,3'-(1,4-Phenylene)bis(3'-ethynyl-1,1'-binaphthalene-2,2'-diyl Phos-
phate) ((‡)-(S,S)-32). To (‡)-(S,S)-40 (32 mg, 0.046 mmol) in dry CH2Cl2 (30 ml), POCl3 (0.2m soln. in
CH2Cl2, 1.0 ml, 0.20 mmol) and Et3N (0.29 g, 0.40 ml, 2.8 mmol) were added at 208 under N2, and the soln. was
stirred for 3 h. After evaporation, THF (10 ml) and H2O (10 ml) were added, and the mixture was stirred for
12 h at 308. Evaporation in vacuo, followed by addition of CH2Cl2 (25 ml) and H2O (20 ml), provided an org.
phase, which was separated and washed with H2O (3 Â 20 ml), dried (Na2SO4), and evaporated in vacuo. CC
‡
(SiO2; CH2Cl2/Et3N 97:3) and ion-exchange chromatography (Dowex 50WX8, Bu4N ; CH2Cl2/MeCN 1 :1)
gave (‡)-(S,S)-32 (34 mg, 55% (from (S,S)-39)). Yellow foam. M.p. >2508. [a]rD:t: ˆ ‡164.7 (c ˆ 0.5, CHCl3). IR
(KBr): 2961m, 2922w, 2874w, 2100w, 1617w, 1482w, 1461w, 1416m, 1386w, 1381w, 1351w, 1297s, 1245m, 1195w,
1150w, 1104s, 1054w, 1024w, 979w, 952w, 893w. 1H-NMR (500 MHz, CDCl3): 0.61 (t, J ˆ 7.3, 24 H); 0.89 ± 1.04 (m,
16 H); 1.07 ± 1.25 (m, 16 H); 2.61 ± 2.81 (m, 16 H); 3.28 (s, 2 H); 7.11 ± 7.21 (m, 8 H); 7.31 ± 7.41 (m, 4 H); 7.78 (d,
J ˆ 8.2, 2 H); 7.94 (d, J ˆ 8.2, 2 H); 8.03 (s, 2 H); 8.08 (s, 2 H); 8.27 (s, 4 H). 13C-NMR (125 MHz, CDCl3): 13.51;
19.37; 23.52; 58.34; 80.28; 81.39; 116.91; 122.36; 123.09; 124.65; 125.62; 126.49; 126.66; 127.54; 127.91; 128.00;
128.21; 128.58; 129.89; 130.46; 130.76; 132.26; 132.67; 134.11; 135.85; 136.87; 148.49; 149.96. 31P-NMR
‡
‡
‡
(121 MHz, CDCl3): 4.61. FAB-MS: 1303 (8, MH ), 1543 (13, [M ‡ Bu4N] ), 242 (100, Bu4N ). HR-FAB-MS:
‡
1300.6804 (M , C82H98N2O8P2; calc. 1300.6798).
(‡)-(S)-3'-(2-{3,5-Bis[3,5-bis(benzyloxy)benzyloxy]phenyl}ethynyl)-2,2'-bis(methoxymethoxy)-3-[2-(tri-
methylsilyl)ethynyl]-1,1'-binaphthalene (G-2-(‡)-(S)-45). To a degassed soln. of G-2-9 (338 mg, 0.40 mmol) in
abs. THF (6 ml) and dry (i-Pr)2NH (5 ml), [PdCl2(PPh3)2] (13.1 mg, 5 mol-%) and CuI (3.5 mg, 5 mol-%) were
added. A degassed soln. of (‡)-(S)-44 (184 mg, 0.37 mmol) in abs. THF (4 ml) was slowly added, and the
resulting mixture heated to 458 for 5 h. After addition of sat. aq. NaCl soln. (20 ml), the aq. phase was extracted
with CH2Cl2 (2 Â 100 ml), and the combined org. phases were dried (Na2SO4) and evaporated in vacuo. CC
(SiO2; hexane/AcOEt 7:1, containing 0.5% Et3N) yielded G-2-(‡)-(S)-45 (308 mg, 69%). M.p. 738. [a]Dr:t:
ˆ
‡50.7 (c ˆ 1.0, CHCl3). IR (KBr): 3058w, 3024w, 2955w, 2922w, 2880w, 2820w, 2149w, 1596s, 1493w, 1450m,
1429m, 1373m, 1344w, 1323w, 1293w, 1245m, 1208w, 1158s, 1053m, 978m, 844m, 751m. 1H-NMR (300 MHz,
CDCl3): 0.31 (s, 9 H); 2.50 (s, 3 H); 2.52 (s, 3 H); 4.94 (d, AB, J ˆ 6.3, 1 H); 4.95 (d, AB, J ˆ 6.3, 1 H); 5.02 (s,
4 H); 5.07 (s, 8 H); 5.21 (d, AB, J ˆ 6.3, 1 H); 5.23 (d, AB, J ˆ 6.3, 1 H); 6.62 (t, J ˆ 2.1, 2 H); 6.65 (t, J ˆ 2.4, 1 H);
6.73 (d, J ˆ 2.1, 4 H); 6.85 (d, J ˆ 2.1, 2 H); 7.22 ± 7.47 (m, 26 H); 7.87 (t, J ˆ 6.9, 2 H); 8.22 (s, 1 H); 8.26 (s, 1 H).
13C-NMR (75 MHz, CDCl3): À0.06; 56.11; 56.22; 70.23; 70.30; 86.51; 93.88; 98.96; 99.14; 99.39; 101.91; 102.14;
103.80; 106.55 (2Â); 110.87; 117.33; 117.37; 124.90; 125.80; 125.84; 126.06; 126.18; 126.84 ; 127.53; 127.62 (2Â);
127.86; 128.10; 128.30; 128.88; 130.45; 130.61; 134.15 (2Â); 134.57; 135.24; 137.08; 139.36; 153.44; 153.73; 160.02;
‡
‡
‡
160.57. MALDI-TOF-MS (CCA): 1247 (11, [MH ‡ K] ), 1231 (96, [MH2 ‡ Na] ), 1230 (100, [MH ‡ Na] ).
Anal. calc. for C79H70O10Si ´ 0.4 AcOEt (1242.76): C 77.90, H 5.94; found: C 77.81, H 5.95.
(‡)-(S)-3'-(2-{3,5-Bis[3,5-bis(benzyloxy)benzyloxy]phenyl}ethynyl)-3-ethynyl-2,2'-bis(methoxymethoxy)-
1,1'-binaphthalene (G-2-(‡)-(S)-46). A soln. of G-2-(‡)-(S)-45 (200 mg, 0.17 mmol) and K2CO3 (81 mg,
0.59 mmol) in THF/MeOH 1 :1 (18 ml) was stirred for 2 h at 208. After addition of H2O (10 ml) and extraction
with CH2Cl2 (3 Â 70 ml), the combined org. phases were dried (Na2SO4) and evaporated in vacuo to give crude
G-2-(‡)-(S)-46. M.p. 658. [a]rD:t: ˆ ‡14.2 (c ˆ 1.0, CHCl3). IR (neat): 3282m, 3066m, 3030m, 2931m, 2867m,
2822w, 2250w, 1595s, 1496m, 1450s, 1429m, 1373s, 1348m, 1321m, 1294m, 1242m, 1204m, 1157s, 1053s, 976s,
909m, 834m, 735m. 1H-NMR (200 MHz, CDCl3): 2.53 (s, 3 H); 2.56 (s, 3 H); 3.36 (s, 1 H); 4.92 (d, AB, J ˆ 6.5,

Helvetica Chimica Acta ± Vol. 83 (2000)
1373
1 H); 4.96 (d, AB, J ˆ 6.5, 1 H); 5.02 (s, 4 H); 5.07 (s, 8 H); 5.14 (d, AB, J ˆ 6.5, 1 H); 5.19 (d, AB, J ˆ 6.5, 1 H);
6.60 (t, J ˆ 2.4, 2 H); 6.62 (t, J ˆ 2.7, 1 H); 6.70 (d, J ˆ 2.1, 4 H); 6.82 (d, J ˆ 2.4, 2 H); 7.21 ± 7.50 (m, 26 H); 7.85
(d, J ˆ 7.2, 2 H); 8.23 (s, 1 H); 8.26 (s, 1 H). 13C-NMR (75 MHz, CDCl3): 53.36; 55.97; 56.03; 70.03; 70.09; 80.58;
81.56; 86.22; 93.68; 98.89; 98.97; 101.69; 103.58; 106.35; 110.65; 116.28; 117.17; 124.628; 125.65; 125.68; 125.78;
126.02; 126.57; 126.62; 127.38; 127.57 (2Â); 127.65; 128.09; 128.67; 130.21; 130.37; 133.85; 134.09; 134.43; 135.29;
‡
‡
136.84; 139.11; 153.23; 153.49; 159.80; 160.33. FAB-MS: 1135 (34, M ), 1104 (100, [M À OMe] ). Anal. calc. for
C76H62O10 ´ H2O (1153.35): C 79.15, H 5.59; found: C 79.38, H 5.84.
(‡)-(S,S)-3,3'-(Buta-1,3-diynediyl)bis[3'-(2-{3,5-bis[3,5-bis(benzyloxy)benzyloxy]phenyl}ethynyl)-2,2'-bis-
(methoxymethoxy)-1,1'-binaphthalene] (G-2-(‡)-(S,S)-47). A soln. of G-2-(‡)-(S)-46 (180 mg, 0.16 mmol) and
CuCl (190 mg, 1.9 mmol) in abs. CH2Cl2 (110 ml) was stirred under dry air for 15 min, and TMEDA (0.28 ml,
0.22 g, 1.9 mmol) was then added. After 1.5 h, H2O (150 ml) was added, and the separated org. phase was
washed with H2O (4 Â 150 ml), dried (Na2SO4), and evaporated in vacuo. GPC (Bio-Beads SX-1) yielded G-2-
(‡)-(S,S)-47 (145 mg, 81%). M.p. 598. [a]rD:t: ˆ ‡280.8 (c ˆ 1.0, CHCl3). IR (neat): 3057m, 3029m, 2984m,
2930m, 2875m, 2824m, 2215w, 1955w, 1708w, 1596s, 1497m, 1451s, 1429s, 1373s, 1347s, 1323m, 1294m, 1266m,
1240m, 1216m, 1202m, 1160s, 1100m, 1057s, 1027m, 978m, 925m, 908m, 834m. 1H-NMR (300 MHz, CDCl3): 2.52
(s, 6 H); 2.63 (s, 6 H); 4.89 (d, AB, J ˆ 6.3, 2 H); 4.96 (d, AB, J ˆ 6.3, 2 H); 4.99 (s, 8 H); 5.04 (s, 16 H); 5.10 (d,
AB, J ˆ 5.9, 2 H); 5.19 (d, AB, J ˆ 5.9, 2 H); 6.58 (t, J ˆ 2.1, 4 H); 6.61 (t, J ˆ 2.1, 2 H); 6.69 (d, J ˆ 2.1, 8 H); 6.81
(d, J ˆ 2.1, 4 H); 7.21 ± 7.44 (m, 52 H); 7.86 (d, J ˆ 8.1, 4 H); 8.24 (s, 2 H); 8.26 (s, 2 H). 13C-NMR (75 MHz,
CDCl3): 56.21; 56.42; 70.22; 70.28; 78.31; 79.73; 86.35; 93.93; 99.13; 99.35; 101.88; 103.79; 106.54; 110.84; 116.31;
117.36; 124.80; 125.77; 125.87; 126.03; 126.35; 126.69; 126.87; 127.63; 127.83 (3Â); 128.10; 128.28; 128.85; 130.45;
130.58; 133.97; 134.51; 134.72; 136.16; 137.03; 139.30; 153.42; 153.94; 159.99; 160.52. MALDI-TOF-MS (CCA):
‡
‡
‡
2292 (100, [MH ‡ Na] ), 2248 (36, [MH ‡ Na À MeOCH2] ), 2203 (13, [MH ‡ Na À 2 MeOCH2] ). Anal. calc.
for C152H122O20 ´ 2H2O (2304.69): C 79.22, H 5.51; found: C 79.23, H 5.67.
(‡)-(S,S)-3,3'-(Buta-1,3-diynediyl)bis[3'-(2-{3,5-bis[3,5-bis(benzyloxy)benzyloxy]phenyl}ethynyl)-2,2'-di-
hydroxy-1,1'-binaphthalene] (G-2-(‡)-(S,S)-48). To G-2-(‡)-(S,S)-47 (180 mg, 0.08 mmol) in THF (35 ml),
conc. HCl (37%, 32 ml) in MeOH (35 ml) was added, and the soln. was stirred for 10 h under N2 at 208. After
addition of H2O (20 ml) and CH2Cl2 (30 ml), the aq. phase was extracted with CH2Cl2 (2 Â 50 ml), and the
combined org. phases were dried (Na2SO4) and evaporated in vacuo to give crude G-2-(‡)-(S,S)-48 (170 mg,
1
98%). Highly viscous oil. [a]rD:t: ˆ ‡312.0 (c ˆ 1.0, CHCl3). H-NMR (300 MHz, CDCl3): 4.98 (s, 8 H); 5.03 (s,
16 H); 5.55 (s, 2 H); 5.84 (s, 2 H); 6.57 (t, J ˆ 2.4, 4 H); 6.62 (t, J ˆ 2.4, 2 H); 6.66 (d, J ˆ 2.1, 8 H); 6.80 (d, J ˆ 2.4,
4 H); 7.17 ± 7.42 (m, 52 H); 7.86 (m, 4 H); 8.22 (s, 2 H); 8.24 (s, 2 H).
Bis(tetrabutylammonium) (‡)-(S,S)-3,3'-(Buta-1,3-diynediyl)bis[3'-(2-{3,5-bis[3,5-bis(benzyloxy)benzyl-
oxy]phenyl}ethynyl)-1,1'-binaphthalene-2,2'-diyl Phosphate] (G-2-(‡)-(S,S)-41). To G-2-(‡)-(S,S)-48 (170 mg,
78 mmol) in dry CH2Cl2 (30 ml), POCl3 (0.16m soln. in CH2Cl2, 2.14 ml, 0.34 mmol) and Et3N (0.47 g, 0.33 g,
4.68 mmol) were added at 208 under N2, and the soln. was stirred for 3 h. After evaporation in vacuo, THF
(15 ml) and H2O (15 ml) were added, and the mixture was stirred for 12 h at 308. Evaporation in vacuo, followed
by addition of CH2Cl2 (30 ml) and H2O (15 ml) provided an org. phase, which was washed with H2O (3 Â 20 ml),
dried (Na2SO4), and evaporated in vacuo. CC (SiO2; CH2Cl2/Et3N 97:3) and ion-exchange chromatography
‡
(Dowex 50WX8, Bu4N ; CH2Cl2/MeCN 1:1) afforded G-2-(‡)-(S,S)-41 (173 mg, 82%). Yellow foam. M.p. 928.
[a]rD:t: ˆ ‡389.5 (c ˆ 1.0, CHCl3). IR (KBr): 3068w, 3036w, 2961m, 2929m, 2865m, 1596s, 1498w, 1450m, 1429w,
1375m, 1343w, 1295m, 1253w, 1205w, 1155s, 1098s, 1050m, 1028m, 895w, 831w, 804w. 1H-NMR (300 MHz,
CDCl3): 0.73 (t, J ˆ 7.3, 24 H); 1.06 ± 1.32 (m, 32 H); 2.81 ± 2.91 (m, 16 H); 4.98 (s, 8 H); 5.03 (s, 16 H); 6.55 ± 6.57
(m, 6 H); 6.70 (d, J ˆ 2.2, 8 H); 6.91 (d, J ˆ 2.3, 4 H); 7.17 ± 7.42 (m, 52 H); 7.79 (d, J ˆ 8.2, 2 H); 7.80 (d, J ˆ 8.2,
2 H); 8.09 (s, 2 H); 8.13 (s, 2 H). 13C-NMR (125 MHz, CDCl3): 13.67; 19.51; 23.68; 58.19; 69.99; 70.11; 78.35;
79.72; 86.38; 93.42; 101.61; 103.07; 106.39; 111.04; 116.59; 118.27; 122.27; 123.08; 124.88; 125.05; 125.44; 126.40;
126.51; 126.97; 127.02; 127.54; 127.95; 128.53; 129.15; 129.20; 129.92; 130.01; 132.17; 132.97; 133.71; 135.09;
136.77; 139.26; 150.07; 150.15 (d, J(31P, 13C) ˆ 9.1); 159.38; 160.11. 31P-NMR (121 MHz, CDCl3): 4.47. ESI-MS
(negative-ion mode): 2457 (8, [M À Bu4N]À), 2237 (3, [M À 2 Bu4N ‡ Na]À), 1107 (100, [M À 2 Bu4N]2À). Anal.
calc. for C176H174N2O20P2 ´ 4H2O (2771.36): C 76.28, H 6.62, N 1.01; found: C 76.29, H 6.70, N 1.10.
(‡)-(S,S)-3,3'-(1,4-Phenylene)bis[3'-(2-{3,5-bis[3,5-bis(benzyloxy)benzyloxy]phenyl}ethynyl)-2,2'-bis(me-
thoxymethoxy)-1,1'-binaphthalene] (G-2-(‡)-(S,S)-49). To a degassed mixture of G-2-9 (330 mg, 0.39 mmol),
[PdCl2(dppf)] (11 mg, 10 mol-%), and CuI (2 mg, 10 mol-%) in (i-Pr)2NH (2 ml) and abs. THF (3 ml) at 408, a
soln. of (‡)-(S,S)-39 (100 mg, 0.13 mmol) in abs. THF (2 ml) was added slowly (30 min). After stirring for 4 h at
408, sat. aq. NaCl soln. (10 ml) was added, and the mixture was extracted with CH2Cl2 (3 Â 50 ml). The
combined org. phases were dried (Na2SO4), and the solvent was evaporated in vacuo. GPC (Bio-Beads SX-1)
yielded G-2-(‡)-(S,S)-49 (140 mg, 48%). Yellow foam. M.p. 1008. [a]rD:t: ˆ ‡146.3 (c ˆ 1.0, CHCl3). IR (neat):

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Helvetica Chimica Acta ± Vol. 83 (2000)
3057m, 3033m, 2924m, 2875m, 2826m, 2215w, 1596s, 1494w, 1449s, 1428m, 1374m, 1345m, 1321w, 1296m, 1263w,
1242m, 1157s, 1101w, 1076m, 1056s, 1027m, 985m, 964m, 923w, 907w, 836m. 1H-NMR (500 MHz, CDCl3): 2.26 (s,
6 H); 2.65 (s, 6 H); 4.39 (d, AB, J ˆ 6.2, 2 H); 4.43 (d, AB, J ˆ 6.3, 2 H); 5.00 (s, 8 H); 5.05 (s, 16 H); 5.05 (d, AB,
J ˆ 6.0, 2 H); 5.18 (d, AB, J ˆ 6.0, 2 H); 6.59 (t, J ˆ 2.3, 4 H); 6.62 (t, J ˆ 2.3, 2 H); 6.69 (d, J ˆ 2.1, 8 H); 6.84 (d,
J ˆ 2.1, 4 H); 7.26 ± 7.46 (m, 52 H); 7.87 (d, J ˆ 8.1, 2 H); 7.89 (s, 4 H); 7.94 (d, J ˆ 8.1, 2 H); 8.05 (s, 2 H); 8.25 (s,
2 H). 13C-NMR (125 MHz, CDCl3): 55.84; 56.12; 70.06; 70.12; 86.44; 93.59; 98.61; 98.92; 101.67; 103.52; 106.33;
110.65; 117.26; 124.64; 125.31; 125.50; 125.97; 126.37; 126.47; 126.59; 126.73; 127.16; 127.54 (2Â); 127.86; 127.98;
128.56; 129.61; 130.36; 130.84; 130.87; 133.52; 134.02; 134.25; 134.81; 136.75; 138.04; 139.03; 151.40; 152.97;
‡
‡
159.66; 160.20. MALDI-TOF-MS (CCA): 2321 (100, [MH ‡ Na] ), 2337 (35, [MH ‡ K] ). Anal. calc. for
C
154H126O20 ´ 3H2O (2350.76): C 78.69, H 5.66; found: C 78.47, H 5.74.
(‡)-(S,S)-3,3'-(1,4-Phenylene)bis[3'-(2-{3,5-bis[3,5-bis(benzyloxy)benzyloxy]phenyl}ethynyl)-1,1'-binaph-
thalene-2,2'-diol] (G-2-(‡)-(S,S)-50). To G-2-(‡)-(S,S)-49 (180 mg, 0.078 mmol) in THF (30 ml), conc. HCl
(37%, 100 ml) in MeOH (30 ml) was added, and the soln. was stirred for 10 h under N2 at 208. H2O (20 ml) and
CH2Cl2 (30 ml) were added, the aq. phase was extracted with CH2Cl2 (2 Â 50 ml), and the combined org. phases
were dried (Na2SO4) and evaporated in vacuo to give crude G-2-(‡)-(S,S)-50 (170 mg, 100%). 1H-NMR
(300 MHz, CDCl3): 4.98 (s, 8 H); 5.03 (s, 16 H); 6.58 (t, J ˆ 2.1, 4 H); 6.63 (t, J ˆ 2.1, 2 H); 6.68 (d, J ˆ 2.1, 8 H);
6.83 (d, J ˆ 2.1, 4 H); 7.18 (d, J ˆ 8.0, 2 H); 7.26 ± 7.43 (m, 50 H); 7.87 (s, 4 H); 7.89 (d, J ˆ 8.0, 2 H); 7.94 (d, J ˆ
8.0, 2 H); 8.07 (s, 2 H); 8.24 (s, 2 H) (OH signals are not visible).
Bis(tetrabutylammonium) (‡)-(S,S)-3,3'-(1,4-Phenylene)bis[3'-(2-{3,5-bis[3,5-bis(benzyloxy)benzyloxy]-
phenyl}ethynyl)-1,1'-binaphthalene-2,2'-diyl Phosphate] (G-2-(‡)-(S,S)-42). To G-2-(‡)-(S,S)-50 (170 mg,
0.078 mmol) in dry CH2Cl2 (30 ml), POCl3 (0.2m soln. in CH2Cl2, 1.66 ml, 0.33 mmol) and Et3N (0.46 g,
0.66 ml, 0.45 mmol) were added at 208 under N2, and the soln. was stirred for 3 h. Evaporation in vacuo, followed
by addition of THF (15 ml) and H2O (15 ml), afforded a mixture, which was stirred for 12 h at 308. After
evaporation of THF in vacuo, CH2Cl2 (30 ml) and H2O (15 ml) were added, and the phases were separated. The
org. phase was washed with H2O (3 Â 20 ml), dried (Na2SO4), and evaporated in vacuo. CC (SiO2; CH2Cl2/Et3N
‡
98 :2) and ion-exchange chromatography (Dowex 50WX8, Bu4N ; CH2Cl2/MeCN 1:1) gave G-2-(‡)-(S,S)-42
(168 mg, 79%). Yellow foam. M.p. 1208. [a]rD:t: ˆ ‡172.8 (c ˆ 0.5, CHCl3). IR (KBr): 3059w, 3030w, 2960m,
2929m, 2871m, 1596s, 1493w, 1450m, 1426w, 1373m, 1344w, 1294m, 1252w, 1204w, 1155s, 1098s, 1050m, 988w,
1
964w, 887w, 834m, 810w. H-NMR (300 MHz, CDCl3): 0.57 (t, J ˆ 7.3, 24 H); 0.90 ± 0.99 (m, 16 H); 1.03 ± 1.14
(m, 16 H); 2.59 ± 2.72 (m, 16 H); 4.98 (s, 8 H); 5.03 (s, 16 H); 6.55 ± 6.57 (m, 6 H); 6.69 (d, J ˆ 2.2, 8 H); 6.92 (d,
J ˆ 2.3, 4 H); 7.14 ± 7.42 (m, 52 H); 7.80 (d, J ˆ 8.4, 2 H); 7.92 (d, J ˆ 8.4, 2 H); 8.03 (s, 2 H); 8.13 (s, 2 H); 8.31 (s,
4 H). 13C-NMR (125 MHz, CDCl3): 13.67; 19.51; 23.68; 58.19; 69.99; 70.11; 78.35; 79.72; 86.38; 93.42; 101.61;
103.07; 106.39; 111.04; 116.59; 118.27; 122.27; 123.08; 124.88; 125.05; 125.44; 126.40; 126.51; 126.97; 127.02;
127.54; 127.95; 128.53; 129.15; 129.20; 129.92; 130.01; 132.17; 132.97; 133.71; 135.09; 136.77; 139.26; 150.07;
150.15 (d, J(31P, 13C) ˆ 9.1); 159.38; 160.11. 31P-NMR (121 MHz, CDCl3): 4.68. MALDI-TOF-MS: 2972 (100,
‡
‡
[MH2 ‡ Bu4N] ), 2730 (11, MH2 ). Anal. calc. for C178H178N2O20P2 (2727.31): C 78.39, H 6.58, N 1.03; found:
C 78.21, H 6.75, N 1.07.
(‡)-(S,S)-3,3'-(Buta-1,3-diynediyl)bis(3'-{2-[3,5-bis(3,5-bis{2-[2-(2-methoxyethoxy)ethoxy]ethoxy}benzyl-
oxy)phenyl]ethynyl}-2,2'-bis(methoxymethoxy)-1,1'-binaphthalene) (G-1-(‡)-(S,S)-51). To a degassed mixture
of G-1-11 (234 mg, 0.22 mmol), [PdCl2(PPh3)2] (6.4 mg, 10 mol-%), and CuI (1.7 mg, 10 mol-%) in (i-Pr)2NH
(2.3 ml) and abs. THF (3 ml), a soln. of (‡)-(S,S)-33 (84 mg, 0.1 mmol) in abs. THF (2.1 ml) was slowly added at
408, and the mixture was stirred for 4 h at 408. Sat. aq. NaCl soln. (10 ml) was added, and the mixture was
extracted with CH2Cl2 (3 Â 50 ml). The combined org. phases were dried (Na2SO4), and the solvent was
evaporated in vacuo. GPC (Bio-Beads SX-1) yielded G-1-(‡)-(S,S)-51 (83 mg, 34%). Highly viscous, yellow oil.
[a]rD:t: ˆ ‡200.2 (c ˆ 1.0, CHCl3). IR (neat): 3055w, 2928s, 2876s, 1596s, 1449m, 1351m, 1322m, 1297m, 1244m,
1157s, 1105s, 1073m, 977m, 929w, 843w. 1H-NMR (300 MHz, CDCl3): 2.54 (s, 6 H); 2.65 (s, 6 H); 3.37 (s, 24 H);
3.52 ± 3.57 (m, 16 H); 3.63 ± 3.76 (m, 48 H); 3.82 ± 3.87 (m, 16 H); 4.10 ± 4.15 (m, 16 H); 4.89 (d, AB, J ˆ 6.2,
2 H); 4.94 ± 4.97 (m, 10 H); 5.09 (d, AB, J ˆ 6.2, 2 H); 5.18 (d, AB, J ˆ 5.8, 2 H); 6.46 (t, J ˆ 2.2, 4 H); 6.59 ± 6.62
(m, 10 H); 6.79 (d, J ˆ 2.0, 4 H); 7.19 ± 7.37 (m, 8 H); 7.41 ± 7.48 (m, 4 H); 7.87 (d, J ˆ 7.8, 4 H); 8.24 (s, 2 H); 8.26
(s, 2 H). 13C-NMR (75 MHz, CDCl3): 56.19; 56.42; 59.15; 67.66; 69.81; 70.22; 70.70; 70.80; 70.96; 72.08; 78.26;
79.73; 86.31; 93.90; 99.09; 99.32; 101.41; 103.70; 106.28; 110.74; 116.31; 117.36; 124.77; 125.71; 125.85; 126.01;
126.34; 126.66; 126.86; 127.62; 127.89 (2Â); 128.08; 130.43; 130.56; 133.94; 134.49; 134.77; 136.16; 139.10; 153.35;
‡
153.87; 160.00; 160.44. MALDI-TOF-MS (CCA): 2741 (100, [MH2 ‡ Na] ).
(‡)-(S,S)-3,3'-(Buta-1,3-diynediyl)bis(3'-{2-[3,5-bis(3,5-bis{2-[2-(2-methoxyethoxy)ethoxy]ethoxy}benzyl-
oxy)phenyl]ethynyl}-1,1'-binaphthalene-2,2'-diol) (G-1-(‡)-(S,S)-52). To G-1-(‡)-(S,S)-51 (83 mg, 0.031 mmol)
in THF (14 ml), conc. HCl (37%, 50 ml) in MeOH (14 ml) was added, and the mixture was stirred for 12 h under

Helvetica Chimica Acta ± Vol. 83 (2000)
1375
N2. After addition of H2O (30 ml), the aq. phase was extracted with CH2Cl2 (3 Â 50 ml), and the combined org.
phases were dried (MgSO4) and evaporated in vacuo to give crude G-1-(‡)-(S,S)-52 (77 mg, 98%). Highly
viscous oil. 1H-NMR (300 MHz, CDCl3): 3.35 (s, 24 H); 3.52 ± 3.56 (m, 16 H); 3.63 ± 3.76 (m, 48 H); 3.80 ± 3.85
(m, 16 H); 4.09 ± 4.14 (m, 16 H); 4.99 (s, 8 H); 6.01 (s, 2 H); 6.11 (s, 2 H); 6.46 (t, J ˆ 2.2, 4 H); 6.60 (d, J ˆ 2.4,
8 H); 6.64 (t, J ˆ 2.6, 2 H); 6.81 (d, J ˆ 2.6, 4 H); 7.15 (d, J ˆ 8.0, 4 H); 7.32 ± 7.43 (m, 8 H); 7.85 ± 7.89 (m, 4 H);
8.23 (s, 2 H); 8.25 (s, 2 H).
Bis(tetrabutylammonium)
(‡)-(S,S)-3,3'-(Buta-1,3-diynediyl)bis(3'-{2-[3,5-bis(3,5-bis{2-[2-(2-methoxy-
ethoxy)ethoxy]ethoxy}benzyloxy)phenyl]ethynyl}-1,1'-binaphthalene-2,2'-diyl Phosphate) (G-1-(‡)-(S,S)-43).
To G-1-(‡)-(S,S)-52 (80 mg, 31 mmol) in dry CH2Cl2 (12 ml), POCl3 (0.16m soln. in CH2Cl2, 0.86 ml,
0.136 mmol) and Et3N (0.26 ml, 0.19 g, 1.89 mmol) were added at 208 under N2, and the soln. was stirred for
4.5 h. Evaporation in vacuo was followed by addition of THF (6 ml) and H2O (6 ml), and the resulting mixture
was stirred for 12 h at 408. THF was evaporated in vacuo, and the aq. phase was extracted with CH2Cl2 (3 Â
20 ml). The combined org. phases were washed with H2O (40 ml), dried (MgSO4), and evaporated in vacuo.
After CC (SiO2; CH2Cl2/Et3N 95 :5), the product was dissolved in CH2Cl2 (15 ml), and the soln. was washed
with H2O (10 ml). The org. phase was dried (MgSO4) and the solvent evaporated in vacuo. Ion-exchange
‡
chromatography (Dowex 50WX8, Bu4N ; CH2Cl2/MeCN 1:1) afforded G-1-(‡)-(S,S)-43 (34 mg, 35%). Highly
viscous, yellow oil. [a]rD:t: ˆ ‡339.4 (c ˆ 1.0, CHCl3). IR (neat): 3056w, 2922s, 2864s, 2214w, 2147w, 1596s, 1448s,
1351m, 1298s, 1250m, 1169s, 1140s, 1099s, 1064s, 896m, 858m, 805m. 1H-NMR (300 MHz, CDCl3): 0.76 (t, J ˆ 7.2,
24 H); 1.13 ± 1.27 (m, 16 H); 1.30 ± 1.40 (m, 16 H); 2.96 ± 2.99 (m, 16 H); 3.35 (s, 24 H); 3.51 ± 3.54 (m, 16 H);
3.58 ± 3.72 (m, 48 H); 3.82 (t, J ˆ 4.8, 16 H); 4.10 (t, J ˆ 4.8, 16 H); 4.94 (s, 8 H); 6.43 (m, 4 H); 6.55 (t, J ˆ 2.3,
2 H); 6.58 (d, J ˆ 1.8, 8 H); 6.88 (d, J ˆ 1.8, 4 H); 7.18 ± 7.24 (m, 8 H); 7.35 ± 7.41 (m, 4 H); 7.81 ± 7.85 (m, 4 H);
8.14 (s, 2 H); 8.15 (s, 2 H). 13C-NMR (125 MHz, CDCl3): 13.64; 19.54; 23.77; 58.41; 58.97; 67.49; 69.63; 70.02;
70.51; 70.59; 70.75; 71.88; 78.30; 79.88; 86.40; 93.34; 101.22; 103.09; 106.12; 110.91; 116.48; 118.05; 122.23;
123.10; 124.83; 125.06; 125.40; 126.38; 126.50; 126.95; 127.02; 127.91; 128.03; 129.95; 130.08; 132.25; 132.97;
133.83; 135.24; 139.02; 149.90; 150.10 (d, J(31P, 13C) ˆ 9.4); 149.93 (d, J(31P, 13C) ˆ 8.7); 160.03. 31P-NMR
‡
‡
(121 MHz, CDCl3): 4.47. MALDI-TOF-MS (HABA): 3391 (65, [M ‡ Bu4N] ), 3149 (100, MH ), 2727 (46,
‡
‡
‡
[MH ‡ Na ‡ K À 2 Bu4N] ), 2709 (48, [MH ‡ 2 Na À 2 Bu4N] ), 2688 (75, [MH2 ‡ Na À 2 Bu4N] ). MALDI-
TOF-MS (HABA; negative-ion mode): 3146 (4, MÀ); 2906 (72, [MH À Bu4N]À); 2687 (78, [MH ‡ Na À
2 Bu4N]À), 2664 (100, [MH2 À 2 Bu4N]À).
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