Regioselective double capping of cyclodextrin scaffolds

Article abstract of DOI:10.1002/chem.201002541

Four different regioselective double capping reactions were applied either to α- or β-cyclodextrin (CD) scaffolds. The first, which relied on the use of a rigid, bulky dialkylating reagent containing two trityl-like subunits, gave access to an A,B,D,E-tet

Full text of DOI:10.1002/chem.201002541

FULL PAPER
DOI: 10.1002/chem.201002541
Regioselective Double Capping of Cyclodextrin Scaffolds
Rafael Gramage-Doria,[a] David Rodriguez-Lucena,[a] Dominique Armspach,*[a]
Coraline Egloff,[a] Matthieu Jouffroy,[a] Dominique Matt,*[a] and Loꢀc Toupet[b]
Abstract: Four different regioselective
double capping reactions were applied
either to a- or b-cyclodextrin (CD)
scaffolds. The first, which relied on the
use of a rigid, bulky dialkylating re-
agent containing two trityl-like subu-
nits, gave access to an A,B,D,E-tetra-
functionalised b-CD regioisomer in
large scale reactions. Two further cap-
ping reactions, involving the dianions
PhP2À and S2À, led to the synthesis of
new C1-symmetrical b-cyclodextrins in
which pairs of neighbouring glucose
units are linked by very short spacers.
The last double capping reaction de-
scribed allowed the high-yield prepara-
tion of unprecedented a- and b-cyclo-
dextrins containing two sulfate handles.
Proximal capping turned out to be fav-
oured for each of the above difunction-
al reagents. The structural characterisa-
tion of the capped species was achieved
by thorough NMR investigations as
well as by single-crystal X-ray diffrac-
tion studies.
Keywords: cavitands
·
cyclodex-
trins · ligand design · macrocyclic
ligands · regioselectivity
Introduction
step syntheses involving two non-consecutive debenzylation
steps.[11] In the case of perbenzylated species, deprotection
usually takes place at the primary rim, although the O-3 po-
The past decade has seen renewed interest in the chemical
modification of cyclodextrins (CDs) as very selective meth-
ods have become available for differentiating the many
identical hydroxyl groups present in these naturally occur-
ring cyclic oligosaccharides.[1] Access to specific regioisomers
in gram-scale quantities is of paramount importance[2] for
taking full advantage of the ubiquitous CD cavity, in partic-
ular, for topics such as supramolecular chemistry[3] and cat-
alysis.[4–7] So far, most of the methods developed for discrim-
inating between identical hydroxyl groups focussed on dis-
ubstituted CDs.[1,8] The more challenging task of obtaining
tetrafunctionalised species in a regioselective manner has
been recently addressed by several groups. For example,
one-step diisobutylaluminum hydride (DIBAL-H) induced
deprotections of perbenzylated[9] CDs have been employed
to produce tetrafunctionalised a-, b- and g-CDs in low to
moderate yields, but with high regioselectivity.[10] Tetrafunc-
tionalised a- and b-CDs are also accessible through multi-
À
sitions of the secondary rim are also affected by C O bond
cleavage for the more sterically demanding perbenzylated
a-CD.[12] On the other hand, permethylated b-CD undergoes
tetrademethylation solely at the secondary rim.[13,14] Another
strategy that has been applied to a-CD, consists of reacting
the cyclic oligosaccharide with an excess of bulky monoalky-
lating agents such as trityl[15,16] or supertrityl chlorides,[17]
thereby giving rise to tetrasubstituted species at the primary
rim with good regioselectivity. Surprisingly, little attention
has been paid to double capping reactions for targeting tet-
rasubstituted CDs since the early work of Tabushi, who
relied on the use of rigid disulfonyl chlorides.[18–20] In the
present paper, we describe a short and convenient synthesis
of a 6A,6B:6D,6E-doubly capped b-CD, which provides easy
access to valuable 6A,6B,6D,6E-functionalised b-CDs in gram-
scale quantities. Capping methodology was also used for the
preparation of new a- and b-CD-derived phosphanes, phos-
phane oxides, thioethers and sulfates.
[a] R. Gramage-Doria, Dr. D. Rodriguez-Lucena, Prof. D. Armspach,
C. Egloff, M. Jouffroy, Dr. D. Matt
Laboratoire de Chimie Inorganique et Catalyse
Institut de Chimie UMR 7177 CNRS
Universitꢀ de Strasbourg
Results and Discussion
Tetrafunctionalisation of native b-CD: Our strategy for the
preparation of A,B,D,E-tetrasubstituted b-CDs relied on the
use of a particular alkylating reagent, namely “bis-trityl” di-
chloride 1. As shown recently, alkylation of b-CD with one
equivalent of 1 and subsequent methylation of the non-alky-
lated hydroxyl groups led to the A,B-capped CD 2.[21] We
anticipated that the use of two equivalents of 1 for the first
alkylation step would regioselectively lead to an A,B:D,E
doubly capped b-CD, as a result of both the capacity of the
difunctional reagent to strap adjacent glucose units and the
67008 Strasbourg cedex (France)
Fax : (+33) 3-68-851-637
E-mail: d.armspach@unistra.fr
dmatt@unistra.fr
[b] L. Toupet
Institut de Physique de Rennes UMR 6251 CNRS
Universitꢀ de Rennes1
Campus de Beaulieu - Bꢁtiment 11 A
35042 Rennes cedex (France)
Supporting information for this article is available on the WWW
under http://dx.doi.org/10.1002/chem.201002541.
Chem. Eur. J. 2011, 17, 3911 – 3921
ꢂ 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
3911

tected (see below). The product was conveniently separated
from over- and under-tritylated species as well as non-
bridged species by standard column chromatography. Note
that applying the same reaction conditions to the smaller a-
CD were rather ineffective because they led to only very
small amounts of doubly capped compound.[22] Clearly, only
a wide enough macrocyle, such as the b-CD torus is able to
accommodate two such large handles.
Characterisation of 3: The formation of a doubly capped
product was inferred from the ESI-MS spectrum of 3, which
showed intense peaks at m/z 2673.4 and 2657.4, with isotopic
profiles exactly as expected for the [M + K]+ and [M +
Na]+ ions, respectively. Proof for A,B,D,E-substitution came
from a single-crystal X-ray diffraction study on the phospho-
rus-containing CD 4 (see Scheme 3), which is derived from
3. The H NMR spectrum of 3 displays 17 singlets arising
from methoxy groups, in agreement with the expected
double cyclisation (Figure 1). The specific formation of A,B
steric bulk of the “bis-trityl” cap, which possibly prevents at-
tachment of two distinct “bis-trityl” units onto adjacent
sugar units. Thus, once an A,B cap is formed, the second
“bis-trityl” unit should form either a D,E or an E,F cap,
with both routes leading to the same regioisomer
(Scheme 1).
1
Scheme 1. Double capping strategy based on the use of the bulky reagent
1.
In fact, doubly capped 3 could be prepared in 50% isolat-
ed yield by reacting b-CD with two equivalents of “bis-
trityl” dichloride 1[21] in pyridine in the presence of 4-(N,N-
dimethylamino)pyridine (DMAP) at 708C, followed by
methylation with NaH/MeI in N,N-dimethylformamide
(DMF) (Scheme 2). Only one doubly capped species was de-
Figure 1. 1H NMR spectrum of 3 recorded in CDCl3 (500.1 MHz) and ex-
pansion showing the 17 singlets for the methoxy groups (top left).
and D,E caps was deduced from a combination of COSY,
TOCSY, HMQC and ROESY experiments (see the Support-
ing Information). Once the connectivity between the indi-
vidual glucose units was established, ROESY experiments
unambiguously showed that a number of the H-6 protons of
the neighbouring capped sugar units correlate with the cen-
tral aromatic proton (Ha or Ha’) of the capping unit; this ob-
servation constituted the ultimate proof for A,B:D,E double
capping (Figure 2). It is worth mentioning here that the aro-
1
matic region of the H NMR spectrum of 3 bears strong re-
semblance to the singly capped-CD 2.[21] In particular, two
low-field signals for the Ha and Haꢃ protons of the central ar-
omatic rings of the “bis-trityl” fragments at d=7.61 and
7.72 ppm, respectively, are typical of non-dangling 6A,6B-cap-
ping units.[21]
Scheme 2. Synthesis of the doubly capped b-CD derivative 3.
3912
www.chemeurj.org
ꢂ 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2011, 17, 3911 – 3921

Capping Cyclodextrin
FULL PAPER
the presence of four triplets at d=2.61, 2.68, 2.78 and
1
2.96 ppm, respectively, in the H NMR spectrum of 8, corre-
sponding to the four non-equivalent hydroxyl protons. As
expected, the reaction of excess Li2PPh in tetrahydrofuran
(THF) with 9 afforded the “introverted” diphosphane 10 as
the major product, together with unidentified side prod-
ucts.[28]
To purify 10, the reaction mixture required treatment
with BH3·THF to afford the protected diphosphane 4, which
was isolated in 40% overall yield from 9 after standard
column chromatography. Removal of the BH3 protecting
groups was carried out quantitatively in boiling HNEt2.[29]
The 31P NMR spectrum of pure diphosphane 10, recorded in
C6D6, displayed two nearly identical singlets at d=À15.2
and À15.0 ppm; values that are typical of dialkylphenylphos-
phanes. The “introverted” character of diphosphane 10 was
revealed by a 31P–31P COSY NMR experiment (Figure 3).
Figure 2. Part of the ROESY spectrum of compound 3 recorded in
CDCl3 at 500.1 MHz. The drawing above the spectrum represents one of
the two capping units (A,B). The arrows represent important through-
space correlations involving the A,B cap. Ha and Haꢃ represent the cen-
tral, endo-oriented aromatic protons of each capping unit.
Double capping of b-CD with dianions: Recent studies on
the double capping of 6A,6B,6D,6E-tetramesylated a-CD 5
with small phenylphosphide,[23,24] or very small sulfide dia-
nions,[25,26] showed that these cyclisation processes are highly
regioselective, even regiospecific (because only adjacent glu-
cose units were being bridged) in the case of the more steri-
cally crowded phenylphosphide, towards 6A,6B:6D,6E-double
capped ligands 6 (TRANSDIP)[27] or 7.[25]
Figure 3. 31P–31P COSY NMR spectrum of diphoshine 10 recorded in
C6D6 at 202.5 MHz.
Although the two non-equivalent phosphorus atoms are too
far apart for significant 31P–31P through-space coupling con-
stants[30] to be observed, the 31P–31P COSY NMR spectrum
displayed correlations between the two P signals, thus prov-
ing that the two phosphorus lone pairs temporarily overlap.
Clearly, the only diastereomer that would be expected to
give rise to the previous observation is the one in which two
phosphorus lone pairs face each other within the cavity.
Interestingly, a rare 31P–13C through-space spin coupling
The synthesis of 6A,6B:6D,6E-doubly capped 3 made it pos-
sible to access further double capping reactions on a b-CD
scaffold. To this end, we first prepared 6A,6B,6D,6E-tetramesy-
lated b-CD 9, which was obtained in 96% yield from 3 after
hydrolysis of the “bis-trityl” caps with aqueous HBF4 in
CH3CN followed by reaction of the intermediate tetrol 8
with methylsulfonylchloride in pyridine/DMAP (Scheme 3).
Evidence for the cleavage of the capping units came from
ACTHNUTRGNEUNG
(TSJ(P,C-6C)=2.6 Hz) was observed between the C-6 atom
Chem. Eur. J. 2011, 17, 3911 – 3921
ꢂ 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemeurj.org
3913

D. Armspach, D. Matt et al.
Scheme 3. Synthesis of the 6A,6B:6D,6E doubly capped diphosphane 10.
of the non-bridged glucose unit C and one of the introverted
P atoms (Figure 4).
Note that, despite its strong basicity, diphosphane 10 is
difficult to oxidise with air, probably because access of
oxygen to the buried phosphorus lone pairs is restricted.
The solid state structure of the phosphane–borane adduct 4
was determined by a single-crystal X-ray diffraction study
(Figure 5).
Figure 5. X-ray structure of the borane–diphosphane adduct 4 (top view).
For clarity, the solvent molecules have been omitted. Important distan-
ces: P1···P2 8.23, B1···B2 4.67 ꢄ.
This study confirmed the bridging of adjacent A,B as well
as D,E glucose units. The cavity, which hosts a molecule of
pentane, has a familiar circular shape, with all the glucose
4
units adopting the standard C1 conformation. The observed
absence of deformation is not surprising because all the
anomeric CD protons resonate within a narrow range (Dd=
1
0.2 ppm) in the H NMR spectrum of 4.[31] Both P–B vectors
Figure 4. 13C{1H} NMR (top) and 13C
{1H,31P} NMR (bottom) spectra of
ACHTUNGTRENNUNG
are almost perpendicular to the axis that runs through the
middle of the cavity and point towards its centre. They are
10 (C6D6, 125.8 MHz) showing the C-6C signal.
3914
www.chemeurj.org
ꢂ 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2011, 17, 3911 – 3921

Capping Cyclodextrin
FULL PAPER
not aligned because of the non-
symmetrical nature of the mole-
cule (angle between the P–B
vectors=146.58). The P···P dis-
tance (8.23 ꢄ) is rather large
compared with that observed in
TRANSDIP. Moreover, the
BH3 protecting groups, which
tend to repel each other, un-
doubtedly increase the P···P
separation. We note also that
one of the phosphorus atoms is
relatively close to the C-6 atom
of the neighbouring C glucose
Scheme 4. Synthesis of the 6A,6B-capped monophosphane 12.
unit
(C-6C···P2
distance=
4.72 ꢄ). This finding is consis-
tent with the existence of a through-space spin coupling be-
tween these two nuclei in diphosphane 10.
Attempts were made to improve the synthesis of 10 by
varying the solvents and temperature of the capping reac-
tion, however, the composition of the reaction mixture
varied little. It should be noted that the first cyclisation is
probably quantitative, as observed for the synthesis of
monophosphane 12, which was obtained from dimesylate
11[32] according to Scheme 4. Oxidation of 12 in air into the
corresponding phosphane oxide 13 occurs readily, in con-
trast to that of diphosphane 10. For storage purposes, 12 is
best converted (see the Supporting Information) into the
borane adduct 14.
Scheme 5. Synthesis of the double sulfur-capped species 15.
doubly capped species, as revealed by the presence of a
unique peak at m/z 1391.6 corresponding to the [M + Na]+
ion.
As for the phosphinidene-capped derivative 10, the
1H NMR spectrum of 15 is in agreement with an overall cir-
cular CD torus, with all anomeric protons lying within a
narrow resonance range (Dd=0.24 ppm). Again, COSY,
TOCSY, HMQC and ROESY experiments recorded at
500.1 MHz were used to establish the molecular structure of
compound 15 (see the Supporting Information). In particu-
lar, these experiments allowed unambiguous identification
of the C-6 atoms linked to a sulfur atom and the corre-
sponding H-6 atoms. S-capping of the A and B units was in-
ferred from ROESY experiments (Figure 6), which showed
the close spatial proximity of the H-6a proton of glucose
unit A and the H-5 proton of the neighbouring glucose unit
B. The same H-6aA atom also correlates with the vicinal H-
5A proton. The observation of both correlations is only con-
sistent with proximal S-capping (see also the Supporting In-
formation). The same type of correlations were observed
within the other pair of capped glucose units, namely D and
With the aim of achieving double capping reactions with a
dianion smaller than the crowded phenylphosphide, we also
decided to synthesise the b-CD version of 7. Treatment of
tetramesylate 9 with the small sulfide dianion in acetone, in
the presence of [18]crown-6, gave the expected 6A,6B:6D,6E-
sulfur-capped CD 15 in 50% isolated yield (Scheme 5). The
ESI mass spectrum of 15 confirmed the formation of a
1
E. Careful examination of the H NMR spectrum of 15 fur-
ther revealed a broadening of some H-6a, H-6b, H-5 and H-
1 signals belonging to capped glucose units, suggesting rapid
conformational mobility of the capped glucose residues.
Chem. Eur. J. 2011, 17, 3911 – 3921
ꢂ 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemeurj.org
3915

D. Armspach, D. Matt et al.
units can also be achieved, provided Bolsꢃs reaction condi-
tions are modified. Indeed, both tetrols 17 and 8 react with
thionyl chloride in CH2Cl2 and NEt3 at low temperature
(À788C) to give a mixture of diastereomeric cyclic disulfites,
the corresponding ESI-MS spectra of which displayed, in
each case, a single signal for the corresponding [M + Na]+
cation. Purification of these mixtures was not necessary be-
cause, in each case, a single product was formed after oxida-
tion with RuCl3/NaIO4, namely disulfate 18 or 19
(Scheme 6). Remarkably, for both a- and b-CD disulfates,
the overall yield was virtually quantitative (95%). Only the
use of a base, with the reaction mixture kept at low temper-
ature, allowed these cyclisations to reach this level of regio-
selectivity.
The regioselectivity of the reaction leading to 18 was un-
ambiguously established by a single-crystal X-ray diffraction
study on this disulfate (Figure 7).
Figure 6. Part of the ROESY spectrum of compound 15 recorded in
CDCl3 at 500.1 MHz. The drawing above the spectrum shows one of the
two capping units (A,B). The arrows represent through-space correla-
tions involving the A,B cap.
Such a feature has previously been detected in another
6A,6B-sulfide-capped methylated b-CD, but not in its 6A,6C
regioisomer,[3] nor in smaller a-CD analogues such as 7.
It should be mentioned here that, beside 15, a minor
product was formed (16; see the Supporting Information),
to which we tentatively assign a A,C:D,G doubly capped
structure. This structural assignment was based on an MS
1
analysis of 16 as well as on its H NMR spectrum, in which
Figure 7. X-ray structure of disulfate doubly capped derivative 18 (view
from the primary rim). For clarity, the solvent molecules that are hydro-
gen-bonded to a sulfate oxygen atom have been omitted. Important dis-
tance: S1···S2 4.01 ꢄ.
the signals of the anomeric protons are much more wide-
spread (Dd=0.93 ppm) than those of 15, thus reflecting a
significant shape distortion of the macrocyclic core brought
about by the A,C:D,G double capping.
Interestingly, the two sulfate caps of 18, which link the
A,B and D,E glucose units, respectively, are intertwined so
as to block the cavity entrance. As for doubly capped CD 4,
the CD macrocycle hosts a molecule of pentane and com-
Cyclodextrins capped with two sulfate moieties: Bols et al.
were recently able to cap benzylated a- and b-CDs with a
sulfate unit linking the 6A and 6D carbon atoms.[33] Double
capping of methylated a- and b-CD scaffolds with sulfate
4
prises glucose units having all undistorted standard C1 con-
Scheme 6. Synthesis of the disulfate doubly capped compounds 18 and 19.
3916
www.chemeurj.org
ꢂ 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2011, 17, 3911 – 3921

Capping Cyclodextrin
FULL PAPER
1,3-Bis
11[32] were synthesised according to literature procedures.
[bis(4-tert-butylphenyl)chloromethyl]benzene (1)[21] and dimesylate
ACHTUNGTRENNUNG
formations. However, those that are capped (A,B,D,E) are
tilted towards the cavity interior. The cavity adopts a slightly
elongated shape, the longest O(4)–O’(4) distance being
8.95 ꢄ, and the shortest being 8.00 ꢄ.
6A,6B:6D,6E-Tetra-O-bis{benzene-1,3-bis
ACTHUNTGRENNG[U bis(4-tert-butylphenyl)methyl]}-
2A,2B,2C,2D,2E,2F,2G,3A,3B,3C,3D,3E,3F,3G,6C,6F,6G-heptadeca-O-methyl-b-cy-
clodextrin (3): Labelling of aromatic protons in the A,B cap (noted with
a prime in the corresponding D,E cap):
The capping mode in 19 was established by NMR analysis.
Consistent with caps involving neighbouring glucose units,
the H-1 protons of 19 resonate within a narrow range of
chemical shifts (Dd=0.3 vs. 0.15 ppm for 18; see the Sup-
porting Information), in agreement with the presence of un-
distorted glucose units.[31] Again, full structural characterisa-
tion was achieved through combined COSY, TOCSY,
HMQC and ROESY studies (see the Supporting Informa-
tion). As for 15, ROESY cross peaks arising from through-
space correlations between the H-6a proton of capped glu-
cose unit A and two H-5 protons, namely H-5A and H-5B,
unequivocally establish that proximal capping had occurred.
Similar correlations could be seen between a H-6a atom of
capped glucose D and H-5D and H-5E. Interestingly, the
ROESY spectrum also showed a spatial proximity between
the H-6b proton of glucose unit A and H-6a of glucose unit
B, suggesting a high degree of flexibility of the AB cap.
Compound 1 (5.42 g, 7.7 mmol) was added to a solution of b-CD (3.97 g,
3.5 mmol) and DMAP (0.51 g, 4.2 mmol) in pyridine (90 mL). The reac-
tion mixture was stirred at 708C for 12 h before being cooled to room
temperature. Pyridine was then removed in vacuo and water (500 mL)
was added to the residue to produce a suspension, which was filtered.
The cake was dried in vacuo at 508C for 12 h. The colourless solid was
dissolved in DMF (150 mL) and NaH (5.88 g, 147 mmol) was added care-
fully, followed by the addition of
a catalytic amount of imidazole
(0.010 g, 0.15 mmol). The reaction mixture was stirred at room tempera-
ture for 1 h before being cooled at 08C. MeI (17.88 g, 7.8 mL, 126 mmol)
was added dropwise at 08C and the yellow suspension thus formed was
stirred for 12 h at room temperature. MeOH (50 mL) was added slowly
to quench excess NaH, and the reaction mixture was poured into water
(500 mL) under stirring before being extracted with Et2O (3ꢆ300 mL).
The organic extract was dried (MgSO4) and evaporated to dryness to
afford a brown residue. The crude material was purified by column chro-
matography (SiO2; petroleum ether/AcOEt, 80:20 to 65:35, v/v) to give
the desired product 3 (4.63 g, 50%) as a colourless solid. Rf =0.60 (SiO2;
petroleum ether/AcOEt, 60:40, v/v); m.p. >2508C (decomp); 1H NMR
Conclusion
The present study has shown that double capping is a pow-
erful means of tetrasubstituting native b-CD, as well as for
introducing useful functionalities on methylated CDs. The
introverted diphosphane 10 and the doubly sulfur-capped 15
constitute prototypes of a new class of bidentate ligands, the
coordination chemistry and catalytic properties of which are
currently under investigation. Furthermore, the cyclic sul-
fates reported in this study are promising starting materials
for the tridifferentiation of methylated cyclodextrins, in par-
ticular as regards the synthesis of CD-based heterotetraden-
tate ligands. Overall, these results usefully complement pre-
vious studies by us and others on the regiofunctionalisation
of cyclodextrins, thereby opening the way to new, cavity-
shaped ligand types.
(500.1 MHz, CDCl3, 258C):
d (assignment by COSY, TOCSY and
ROESY)=1.17 (s, 6H; tBu), 1.18 (s, 6H; tBu), 1.20 (s, 6H; tBu), 1.24 (s,
3
6H; tBu), 1.27–1.29 (48H; tBu), 2.69 (d, J
2.73 (s, 3H; OMe-6G), 2.73 (d, 3J(H-2,H-1)=3.7 Hz, 1H; H-2B), 3.07 (s,
(H-2,H-1)=4.0 Hz, 1H; H-2E),
ACHTUNGTRENNUNG
AHCTUNGTRENNUNG
3H; OMe-6C), 3.25 (s, 3H; OMe-6F), 3.32 (s, 3H; OMe-2B), 3.36 (s, 3H;
OMe-2E), 3.51 (s, 3H; OMe-2G), 3.56 (s, 3H; OMe-2A), 3.58 (s, 3H;
OMe-2F), 3.60 (s, 3H; OMe-2C), 3.62 (s, 3H; OMe-2D), 3.63 (s, 9H;
OMe-3), 3.64 (s, 3H; OMe-3), 3.65 (s, 3H; OMe-3), 3.66 (s, 3H; OMe-3),
3.67 (s, 3H; OMe-3), 3.20–4.05 (m, 38H; H-2, H-3, H-4, H-5, H-6aB,E, H-
3
6A,C,D,F,G), 4.22–4.28 (m, 3H; H-1B, H-6bB,E), 4.49 (d, J
G
1H; H-1E), 5.15 (d, 3J
2)=3.8 Hz, 1H, H-1A), 5.38 (d, 3J
3J(H-1,H-2)=3.9 Hz, 1H; H-1C), 5.49 (d, 3J
1D), 6.96 (d, J
Hb), 6.99 (d, 3J
(Hc’,Hd’)=7.8 Hz, 1H; Hc’), 7.08 (t, 3J
Hc), 7.14–7.29 (m, 17H; Hd, Hf, Hf’, Hh, Hh’, Hj, Hj’, Hl and Hl’), 7.32–7.45
(m, 12H, He, He’, Hi, Hi’, Hk and Hk’), 7.51 (d, 3J(Hg,Hh)=3J
(Hg’,Hh’)=
7.8 Hz, 4H; Hg and Hg’), 7.61 (br s, 1H; Ha), 7.72 ppm (br s, 1H; Ha’);
13C{1H} NMR (75.5 MHz CDCl3, 258C): d (assignment by HMQC)=31.4
(24C; Me of tBu), 34.3 (8C; C of tBu), 57.8, 57.9, 58.1, 58.1, 58.3, 58.4,
58.8, 59.0, 59.5, 59.7, 60.6, 61.0, 61.5, 61.7, 61.75, 61.84, 62.0 (OMe), 61.68,
61.70, 62.7, 63.2 (C-6A,B,D,E), 71.1, 71.8, 72.5 (C-6C,F,G), 70.46, 70.49, 70.6,
70.8, 71.2, 71.6, 71.7 (C-5), 77.2, 78.7, 80.2, 80.5, 80.98, 81.04, 81.2, 81.3,
81.6, 81.8 (4C), 82.1, 82.2, 82.3, 82.6 (2C), 82.7 (2C), 82.9 (C-2, C-3, C-4),
85.7, 86.1, 87.5, 87.9 [OC(Ar)3], 97.7, 98.2, 98.5, 98.6, 98.8 (3C) (C-1),
124.1 (5C), 124.3, 124.4, 124.5 (2C), 124.6, 126.3, 126.4, 126.5, 126.8,
127.3, 127.5, 128.11, 128.14, 130.5, 131.0, 131.5, 131.9, 134.4, 135.0 (o-C
and m-C), 140.1, 140.2, 140.4, 140.6, 140.9, 141.6, 141.9, 142.4, 142.8,
144.6, 145.0, 145.2, 148.5, 148.52, 148.54, 148.56, 148.60, 148.7 (2C),
148.9 ppm (ipso-C); elemental analysis calcd (%) for C155H212O35·CH2Cl2
G
ACHTUNGTRENNUNG(H-1,H-
AHCTUNGTRENNUNG
R
ACHTUNGTRENNUNG
3
3
Experimental Section
G
ACHTUNGTRENNUNG
E
ACHTUNGTRENNUNG
G
E
ACHTUNGTRENNUNG
General: All manipulations were performed in Schlenk-type flasks under
dry nitrogen. Solvents were dried by conventional methods and distilled
immediately prior to use. CDCl3 was passed down a 5 cm-thick alumina
column and stored under nitrogen over molecular sieves (4 ꢄ). Routine
1H and 13C{1H} spectra were recorded with Bruker FT instruments
N
ACHTUNGTRENNUNG
1
(AVANCE 300, 500, and 600 spectrometers). H NMR spectral data were
referenced to residual protiated solvent (d=7.26 ppm for CDCl3 and d=
7.16 ppm for C6D6); 13C chemical shifts are reported relative to deuterat-
ed solvents (d=77.00 ppm for CDCl3 and d=128.06 ppm for C6D6) and
the 31P NMR data are given relative to external H3PO4. Mass spectra
were recorded either with a ZAB HF VG analytical spectrometer using
m-nitrobenzyl alcohol as matrix or with a Bruker MicroTOF spectrome-
ter (ESI) using CH2Cl2, MeCN or MeOH as solvent. Elemental analyses
were performed by the Service de Microanalyse, Institut de Chimie,
Strasbourg. Melting points were determined with a Bꢅchi 535 capillary
melting point apparatus. All commercial reagents were used as supplied.
Chem. Eur. J. 2011, 17, 3911 – 3921
ꢂ 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemeurj.org
3917

D. Armspach, D. Matt et al.
(2635.32 + 83.95): C 68.88, H 7.93; found: C 68.77, H 8.09; MS (ESI-
pension was slowly cannulated, within 1 h, into a stirred solution of tetra-
mesylate 9 (0.300 g, 0.18 mmol) in THF (25 mL). The reaction mixture
was stirred for 12 h at room temperature, then the solvent was removed
in vacuo and excess Li2PPh was protonated with MeOH (15 mL). After
removal of the solvent in vacuo, toluene (100 mL) was added and the re-
sulting suspension was filtered over Celite. Evaporation of the solvent
gave a colourless residue, which was dissolved in THF (10 mL) before a
solution of BH3·THF (1.00m in THF, 0.9 mL, 0.9 mmol) was added drop-
wise at 08C. After stirring for 12 h at room temperature, the solvent was
removed in vacuo and the resulting colourless residue was subjected to
column chromatography (dried SiO2; CH2Cl2/MeOH, 97:3, v/v) to afford
pure 4 (0.120 g, 40%) as a colourless solid. Rf =0.35 (SiO2; CH2Cl2/
MeOH, 92:8, v/v); m.p. 1858C; 1H NMR (300.1 MHz, CDCl3, 258C): d
(assignment by COSY)=0.89 (br s, 6H; P-BH3), 1.62–1.64 (m, 4H; H-
TOF): m/z (%): 2673.36 (15) [M
+ +
K]+, 2657.38 (78) [M Na]+,
2641.41 (9) [M + Li]+.
2A,2B,2C,2D,2E,2F,2G,3A,3B,3C,3D,3E,3F,3G,6C,6F,6G-Heptadeca-O-methyl-b-cy-
clodextrin (8): HBF4 (34 wt% aq, 7.5 g, 7.5 mL, 29 mmol) was added
dropwise to stirred solution of capped cyclodextrin (2.55 g,
ACHTUNGTRENNUNG
a
3
0.97 mmol) in MeCN (30 mL) at room temperature. After 30 min, NEt3
(1.47 g, 2.0 mL) was added dropwise under stirring. Addition of water
(100 mL) to the reaction mixture caused the carbinol to precipitate. The
resulting suspension was filtered and the filtrate was extracted with
CHCl3 (3ꢆ50 mL). The combined organic extracts were washed with sa-
turated aqueous NaHCO3 (100 mL) then dried (MgSO4). Removal of the
solvent in vacuo gave tetrol 8 (1.32 g, 99%) as a colourless solid. Rf =
1
0.18 (SiO2; CH2Cl2/MeOH, 92:8, v/v); m.p. 1538C; H NMR (300.1 MHz,
or
6aA,B,D,E), 2.89–2.91 (m, 2H; H-6bA,D B,E), 3.17 (s, 3H; OMe), 3.22 (s,
CDCl3, 258C): d (assignment by COSY)=2.61 (t, 3J
ACHTUNGTRENNUNG
3H; OMe), 3.27 (s, 3H; OMe), 3.44 (s, 3H; OMe), 3.45 (s, 6H; OMe),
3.45 (s, 3H; OMe), 3.46 (s, 3H; OMe), 3.53 (s, 6H; OMe), 3.57 (s, 3H;
OMe), 3.59 (s, 3H; OMe), 3.62 (s, 3H; OMe), 3.64 (s, 6H; OMe), 3.67 (s,
3H; OMe), 3.67 (s, 3H; OMe), 3.10–4.27 (m, 34H; H-2, H-3, H-4,
H-5B,E or A,D, H-5C,F,G, H-6bB,E or A,D, H-6C,F,G), 4.60–4.62 (m, 2H; H-5A,D or B,E),
1H; OH), 2.68 (t, 3J
N
ACHTUNGTRENNUNG
AHCTUNGTRENNUNG
7H; H-2), 3.30–4.00 (m, 35H; H-3, H-4, H-5, H-6), 3.37 (s, 9H; OMe),
3.49 (s, 9H; OMe), 3.51 (s, 6H; OMe), 3.52 (s, 3H; OMe), 3.53 (s, 3H;
OMe), 3.62 (s, 9H; OMe), 3.63 (s, 3H; OMe), 3.64 (s, 6H; OMe), 3.65 (s,
4.91 (d, 3J(H-1,H-2)=3.8 Hz, 1H; H-1), 4.94 (d, 3J
ACTHUNTGRNENUG ACHTUNTGERN(NUGN H-1,H-2)=3.3 Hz,
3H; OMe), 5.01–5.03 (m, 2H; H-1), 5.09 (d, 2J
H-1), 5.10 (d, 2J
3.5 Hz, 2H; H-1), 5.23 ppm (d, 2J
ACHTUNGTRENNUNG
2H; H-1), 4.97–5.00 (m, 3H; H-1), 5.11 (d, 3J
ACTHNUTRGNE(UNG H-1,H-2)=3.6 Hz, 1H; H-
G
ACHTUNGTRENNUNG
1), 7.46–7.47 (m, 6H; m-H, p-H), 7.77–7.83 ppm (m, 4H; o-H); 13C{1H}
AHCTUNGTRENNUNG
NMR (75.5 MHz CDCl3, 258C): d (assignment by HMQC)=27.2 (d,
NMR (75.5 MHz CDCl3, 258C): d (assignment by HMQC)=58.3 (3C),
58.7, 58.8, 58.95, 59.00, 59.1, 59.2 (2C), 61.05, 61.09, 61.25, 61.28, 61.5,
61.6, 61.78 (OMe), 61.78, 62.0 (2C), 62.1 (C-6A,B,D,E), 71.2, 71.3, 71.5 (C-
5C,F,G), 71.4, 71.5, 71.7 (C-6C,F,G), 71.8, 72.0, 72.3, 72.5 (C-5A,B,D,E), 78.3,
79.1 (2C), 80.0, 80.4, 80.7, 81.1, 81.2, 81.4, 81.5, 81.6 (2C), 81.7, 81.8
(2C), 82.0 (4C), 82.07, 82.14 (C-2, C-3, C-4), 98.4, 98.6, 98.7 (2C), 98.85
(2C), 98.92 ppm (C-1); elemental analysis calcd for (%) C59H104O35
(1373.44): C 51.60, H 7.63; found: C 51.68, H 7.57; MS (ESI-TOF): m/z
(%): 1395.63 (100) [M + Na]+.
or
1J
1J
N
N
B,E), 34.3 (d,
(C,P)=30.0 Hz), 35.2 (d, 1J
(C,P)=30.0 Hz; C-6B,E
A,D), 57.9 (3C),
or
58.0, 58.2, 58.45, 58.49, 58.7, 58.8, 58.9, 61.5, 61.6 (2C), 61.8, 61.9, 62.20,
or
62.22 (OMe), 64.5, 64.7 (C-5A,D B,E), 68.7 (d, 2J
G
(C,P)=6.4 Hz), 69.0 (d,
2J
(C,P)=5.5 Hz) (C-5B,E A,D), 70.57, 71.2, 71.42 (C-6C,F,G), 70.9, 71.1,
or
71.44 (C-5C,F,G), 80.1, 80.4, 80.5, 81.2, 81.3, 81.5, 81.8, 82.0, 82.3 (5C), 82.4,
82.5, 83.1, 83.3 (C-2, C-3, C-4C,F,G), 86.7 (d, 3J
(C,P)=10.1 Hz), 87.0 (d,
3J(C,P)=10.1 Hz) (C-4A,D or B,E), 89.1, 89.5 (C-4B,E or A,D), 98.46, 98.54, 99.6,
100.3, 100.5, 100.8, 101.2 (C-1), 128.7, 128.9 (m-C), 131.1, 131.2 (p-C),
AHCTUNGTRENNUNG
AHCTUNGTRENNUNG
6A,6B,6D,6E-Tetra-O-methylsulfonyl-2A,2B,2C,2D,2E,2F,2G,-
2
1
131.6 (d, J
ACHUTNGTRENNUG(C,P)=3.7 Hz; o-C), 131.3 (d, JCAHTUNGTRENNNUG
3A,3B,3C,3D,3E,3F,3G,6C,6F,6G-heptadeca-O-methyl-b-cyclodextrin (9): Meth-
anesulfonyl chloride (0.34 g, 0.23 mL, 2.94 mmol) was added to a solution
of tetrol 8 (0.96 g, 0.70 mmol) and DMAP (0.35 g, 2.87 mmol) in anhy-
drous pyridine (30 mL) at 08C. The reaction mixture was stirred at room
temperature for 12 h before adding water (100 mL). The solution was ex-
tracted with AcOEt (3ꢆ50 mL) and the combined organic extracts were
washed sequentially with HCl (2m; 2ꢆ50 mL), NaOH (2m; 2ꢆ50 mL)
and water (50 mL) then dried (MgSO4). Removal of the solvent in vacuo
gave pure tetramesylate 9 (1.14 g, 97%) as a colourless solid. Rf =0.40
(SiO2; CH2Cl2/MeOH, 92:8, v/v); m.p. 2018C; 1H NMR (300.1 MHz,
CDCl3, 258C): d (assignment by COSY)=3.06 (s, 6H; OSO2Me), 3.07 (s,
3H; OSO2Me), 3.08 (s, 3H; OSO2Me), 3.14–3.21 (m, 7H; H-2), 3.37 (s,
3H; OMe), 3.38 (s, 3H; OMe), 3.39 (s, 3H; OMe), 3.49 (s, 9H; OMe),
3.50 (s, 6H; OMe), 3.53 (s, 6H; OMe), 3.60 (s, 3H; OMe), 3.61 (s, 3H;
OMe), 3.62 (s, 6H; OMe), 3.64 (s, 3H; OMe), 3.66 (s, 3H; OMe), 3.68 (s,
3H; OMe), 3.40–4.05 (m, 27H; H-3, H-4, H-5, H-6C,F,G), 4.32–4.34 (m,
2H; H-6aA,D or B,E), 4.53–4.70 (m, 6H; H-6aB,E or A,D, H-6bA,B,D,E), 5.08–5.11
(d, 2J(C,P)=3.7 Hz; o-C), 132.2 ppm (d, 1J
A
ACHTUNGTRENNUNG
31P{1H} NMR (121.5 MHz CDCl3, 258C): d=17.8 (s), 18.4 ppm (s); ele-
mental analysis calcd (%) for C71H116B2O31P2·MeOH (1549.23 + 32.04):
C 54.69, H 7.65; found: C 54.56, H 7.69; MS (ESI-TOF): m/z (%):
1571.71 (100) [M + Na]+.
6A,6B,6D,6E-Tetradeoxy-6A,6B:6D,6E-bis[(R)-phenylphosphinidene]-
2A,2B,2C,2D,2E,2F,2G,3A,3B,3C,3D,3E,3F,3G,6C,6F,6G-heptadeca-O-methyl-b-cy-
clodextrin (10): A solution of 4 (0.080 g, 0.52 mmol) in HNEt2 (8 mL)
was heated to reflux for 12 h. After cooling to room temperature, the sus-
pension was filtered over Celite and the filtrate was evaporated to dry-
ness in vacuo to afford analytically pure 10 (0.080 g, 99%). Rf =0.40
(SiO2; CH2Cl2/MeOH, 92:8, v/v); m.p. 1958C; 1H NMR (300.1 MHz,
CDCl3, 258C): d (assignment by COSY)=1.72–1.74 (m, 2H; H-6aA,D or B,E),
or
1.86–1.88 (m, 2H; H-6aB,E A,D), 2.81 (td, 2J
G
3
13.5 Hz, J
(H-6b,H-5)=3.9 Hz, 2H; H-6bA,D or B,E), 3.05–3.29 (m, 12H; H-
2, H-6aC,F,G, H-6bB,E or A,D), 3.11 (s, 3H; OMe), 3.20 (s, 3H; OMe), 3.27 (s,
3H; OMe), 3.30–3.72 (m, 14H; H-3, H-4), 3.47 (s, 3H; OMe), 3.48 (s,
3H; OMe), 3.49 (s, 3H; OMe), 3.50 (s, 6H; OMe), 3.55 (s, 6H; OMe),
3.60 (s, 3H; OMe), 3.62 (s, 3H; OMe), 3.65 (s, 9H; OMe), 3.66 (s, 6H;
3
3
(m, 4H; H-1), 5.14 (d, J
G
ACHTUNGTRNE(NUNG H-1,H-
2)=3.9 Hz, 1H, H-1), 5.22 ppm (d, 3J
AHCTUNGTRENNUNG
13C{1H} NMR (75.5 MHz CDCl3, 258C): d (assignment by HMQC)=37.2,
37.3 (2C), 37.5 (OSO2Me), 58.3, 58.4 (2C), 58.5, 58.7, 59.1, 59.2 (2C),
59.36, 59.44, 61.1, 61.2, 61.6 (3C), 61.76, 61.80 (OMe), 69.3 (2C), 69.9
(2C) (C-6A,B,D,E), 69.6 (2C), 69.7 (2C) (C-5A,B,D,E), 70.9, 71.0 (2C) (C-
6C,F,G), 71.2 (2C), 71.3 (C-5C,F,G), 78.1, 78.4, 80.1, 80.2, 80.6, 80.7 (2C),
81.0, 81.5, 81.6 (5C), 81.7, 81.8, 81.9 (3C), 81.95, 82.04 (C-2, C-3, C-4),
97.7, 98.4, 98.9 (2C), 99.1 (2C), 99.2 ppm (C-1); elemental analysis calcd
(%) for C63H112O43S4 (1685.80): C 44.89, H 6.70; found: C 44.88, H 6.65;
MS (ESI-TOF): m/z (%): 1707.54 (100) [M + Na]+.
OMe), 3.81–3.42 (m, 8H; H-5A,D B,E, H-5C,F,G, H-6bC,F,G), 4.29–4.31 (m,
or
2H; H-5B,E A,D), 4.95–5.05 (m, 6H, H-1), 5.22 (d, 3J
or
1H; H-1), 7.20–7.28 (m, 6H; m-H, p-H), 7.41–7.51 ppm (m, 4H; o-H);
13C{1H} NMR (125.8 MHz, C6D6, 258C): d (assignment by HMQC)=
28.66 (d, 1J(C,P)=15.4 Hz; C-6A or D), 28.69 (d, 1J(C,P)=16.2 Hz; C-6D or A),
or
or
35.0 (d, 1J(C,P)=19.1 Hz; C-6B E), 35.1 (d, 1J(C,P)=19.7 Hz; C-6E B),
ACTHNUTRGENNUG CAHTUNGTRENNUGN
58.1 (2C), 58.2, 58.3, 58.7, 59.10, 59.14, 59.4, 59.68, 59.74, 61.77, 61.79,
or
61.9, 62.0, 62.1, 62.3 (2C) (OMe), 67.5 (d, 2J
(C,P)=11.7 Hz; C-5A D),
67.6 (d, 2J
TSJ
C-5B E), 74.3 (d, 2J
AHCTUNGTRENNUNG
(C,P)=11.7 Hz; C-5D A), 71.5 (2C), 71.8 (C-5C,F,G), 72.1 (d,
or
P,P’-{6A,6B,6D,6E-Tetradeoxy-6A,6B:6D,6E-bis[(R)-phenylphosphinidene]-
2A,2B,2C,2D,2E,2F,2G,3A,3B,3C,3D,3E,3F,3G,6C,6F,6G-heptadeca-O-methyl-b-cy-
clodextrin} diborane (4): A solution of nBuLi (1.60m in hexane, 1.22 mL,
1.96 mmol) was added dropwise to a stirred solution of H2PPh (0.098 g,
0.098 mL, 0.89 mmol) in THF (16.5 mL) at À788C. The temperature of
the yellow solution was allowed to rise to room temperature over 1 h
whereupon the phosphide dianion precipitated. The resulting yellow sus-
ACHUTNGRENNUG CAHTUNGTRENNUNG
(C,P)=2.6 Hz; C-6C), 72.4 (2C; C-6F,G), 74.0 (d, 2J
or
or
82.42, 82.97, 83.15, 83.23, 83.36 (3C), 83.4, 83.5, 83.6, 84.1, 84.6, 84.7 (C-2,
or
C-3, C-4C,F,G), 87.2 (d, 3J
G
E), 87.3 (d, 3J
ACHTUNGTRENNUNG
or
or
8.0 Hz; C-4E B), 90.2 (d, 3J
G
ACHTUNGTRENNUNG
2.6 Hz; C-4D or A), 99.27, 99.32, 99.7, 99.9, 100.0 (2C), 101.2 (C-1), 128.96,
129.03 (p-C), 129.15 (overlapping d, 3J
AHCTUNGTRENNUNG
3918
www.chemeurj.org
ꢂ 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2011, 17, 3911 – 3921

Capping Cyclodextrin
FULL PAPER
(d, 2J
1J(C,P)=11.7 Hz, 2C; ipso-C); 31P{1H} NMR (202.5 MHz, C6D6, 258C): d
=À15.0 (s), À15.2 ppm (s); elemental analysis calcd (%) for
G
E
81.7 (2C), 81.8, 82.0, 82.1 (3C), 82.2, 82.4, 83.6, 86.1 (C-2, C-3, C-
or
or
G
ACTHNGUTERNNUG
4C,D,E,F,G), 86.2 (d, 3J(C,P)=11.3 Hz; C-4A B), 88.9 (C-4B A), 98.8, 98.9,
99.0, 99.2 (2C), 99.6, 100.3 (C-1), 128.8 (d, 3J
(d, 2J(C,P)=9.1 Hz; o-C), 132.0 (p-C), 135.0 ppm (d, 1J
ACHTUNGTRENNUNG
ACHTUNGTRENNUNG
R
54.82, H 7.35; MS (ESI-TOF): m/z (%): 1521.57 (100) [M + H]+.
ipso-C); 31P{1H} NMR (121.5 MHz, CDCl3, 258C): d=35.9 ppm (s); ele-
mental analysis calcd (%) for C67H111O34P·2CH2Cl2 (1491.55 + 169.86): C
49.88, H 6.98; found: C 50.20, H 7.15; MS (ESI-TOF): m/z (%): 1513.7
[M + Na]+.
6A,6B-Dideoxy-6A,6B-(R)-phenylphosphinidene-2A,2B,2C,2D,2E,2F,2G,-
3A,3B,3C,3D,3E,3F,3G,6C,6D,6E,6F,6G-nonadeca-O-methyl-b-cyclodextrin (12):
A solution of nBuLi (1.60m in hexane, 4.06 mL, 6.50 mmol) was added
dropwise to a stirred solution of H2PPh (0.35 g, 0.35 mL, 3.24 mmol) in
THF (40 mL) at À788C. The temperature of the yellow solution was al-
lowed to rise to room temperature over 1 h, whereupon the phosphide
dianion precipitated. The resulting yellow suspension was slowly cannu-
P-{6A,6B-Dideoxy-6A,6B-(R)-phenylphosphinidene-2A,2B,2C,2D,2E,2F,2G,-
3A,3B,3C,3D,3E,3F,3G,6C,6D,6E,6F,6G-nonadeca-O-methyl-b-cyclodextrin}
borane (14): A solution of BH3·THF (1.00m in THF, 0.31 mL, 0.31 mmol)
was added dropwise to
a solution of monophosphane 12 (0.150 g,
lated, within 1 h, into
a
stirred solution of dimesylate 11 (1.26 g,
0.10 mmol) in THF (10 mL) at 08C. After stirring for 12 h at room tem-
perature, the solvent was removed in vacuo and the resulting colourless
residue was subjected to column chromatography (dried SiO2; CH2Cl2/
MeOH, 97:3, v/v) to afford pure 14 (0.140 g, 95%) as a colourless solid.
Rf =0.35 (SiO2; CH2Cl2/MeOH, 92:8, v/v); m.p. 1838C; 1H NMR
(300.1 MHz, CDCl3, 258C): d=0.70 (br s, 3H; P-BH3), 1.78 (m, 1H; H-
0.81 mmol) in THF (110 mL). The reaction mixture was stirred for 12 h
at room temperature, then the solvent was removed in vacuo and excess
Li2PPh was protonated with MeOH (75 mL). After removal of the sol-
vent in vacuo, toluene (200 mL) was added and the resulting suspension
was filtered over Celite. Evaporation of the solvent to dryness in vacuo
afforded analytically pure 12 (1.16 g, 97%) as a white solid. Rf =0.35
(SiO2; CH2Cl2/MeOH, 92:8, v/v); 1H NMR (300.1 MHz, CDCl3, 258C): d
2
3
6aA or B), 1.98 (m, 1H; H-6aB or A), 2.85 (dd, J(H-6b,H-6a)=13.9 Hz, J
ACHTUNGTRENNUNG(H-
6b,H-5)=4.1 Hz, 1H; H-6bB or A), 3.21 (s, 3H; OMe), 3.26 (s, 3H; OMe),
3.34 (s, 3H; OMe), 3.37 (s, 3H; OMe), 3.42 (s, 3H; OMe), 3.45 (s, 3H;
OMe), 3.48 (s, 9H; OMe), 3.50 (s, 3H; OMe), 3.52 (s, 3H; OMe), 3.54 (s,
3H; OMe), 3.61 (s, 3H; OMe), 3.64 (s, 6H; OMe), 3.65 (s, 3H; OMe),
(assignment by COSY)=1.77 (m, 1H; H-6aA or B), 1.85 (m, 1H; H-6aB or A),
2.86 (t, 2J(H-6b,H-6a)=2J
(H-6b,P)=13.5 Hz, 1H; H-6bA B), 3.16–3.46
or
(m, 17H; H-2, H-3, H-6bB A, H-4A,B), 3.23 (s, 3H; OMe), 3.28 (s, 3H;
OMe), 3.35 (s, 3H; OMe), 3.37 (s, 6H; OMe), 3.47 (s, 3H; OMe), 3.50 (s,
9H; OMe), 3.51 (2ꢆs, 6H; OMe), 3.54 (s, 3H; OMe), 3.61 (s, 3H;
OMe), 3.65 (s, 9H; OMe), 3.66 (s, 6H; OMe), 3.67 (s, 3H; OMe), 3.95–
or
3.68 (s, 9H; OMe), 3.09–4.18 (m, 38H; H-2, H-3, H-4, H-5B or A and C,D,E,F,G
,
or
or
H-6bA B, H-6C,D,E,F,G), 4.50 (m, 1H; H-5A B), 4.94 (d, 3J
3.4 Hz, 1H; H-1), 5.00 (m, 2H; H-1), 5.13 (d, 3J
(H-1,H-2)=2.6 Hz, 1H;
H-1), 5.18 (d, 3J(H-1,H-2)=2.9 Hz, 1H; H-1), 5.26 (d, 3J
(H-1,H-2)=
3.7 Hz, 1H; H-1), 5.32 (d, 3J
(H-1,H-2)=3.3 Hz, 1H; H-1), 7.44–7.48 (m,
ACHTUNGTRENUN(NG H-1,H-2)=
AHCTUNGTRENNUNG
3.32 (m, 20H; H-4C,D,E,F,G, H-5C,D,E,F,G, H-6C,D,E,F,G), 4.00 (m, 1H; H-5A or B),
G
ACHTUNGTRENNUNG
or
4.27 (m, 1H; H-5B A), 5.00 (d, 3J
T
ACHTUNGTRENNUNG
3J
5.11 (d, 3J
1H; H-1), 5.19 (d, J
G
E
ACTHNGUTERNNUG
3H; m-H, p-H), 7.71 ppm (t, 3J(o-H,m-H)=8.3 Hz, 2H; o-H); 13C{1H}
or
A
NMR (75.5 MHz CDCl3, 258C): d=27.9 (d, 1J
(C,P)=34.9 Hz; C-6B A),
3
or
A
34.2 (d, 1J
(C,P)=31.4 Hz; C-6A B), 57.8, 58.1, 58.15, 58.18, 58.5, 58.6,
3.9 Hz, 1H; H-1), 7.30–7.32 (m, 3H, m-H, p-H), 7.44–7.49 ppm (m, 2H,
58.8, 58.9 (2C), 59.0, 59.2, 59.3, 60.9, 61.1, 61.3, 61.5, 61.6, 61.8, 61.9
or
or
o-H); 13C{1H} NMR (75.5 MHz, CDCl3, 258C):
d
(assignment by
(C,P)=18.6 Hz;
ACTHNGUTERNNUG
(OMe), 64.3 (C-5B A), 68.1 (d, 2J(C,P)=6.8 Hz; C-5 A B), 70.2, 70.7
1
1
HMQC)=27.5 (d, J
G
(4C) (C-5C,D,E,F,G), 70.4, 70.9, 71.1 (2C), 71.2 (C-6C,D,E,F,G), 75.9, 78.3, 78.8,
C-6B A), 58.0, 58.25, 58.33, 58.4, 58.7 (3C), 58.9, 59.0 (3C), 59.1, 61.1,
79.9, 80.7, 80.9, 81.6, 81.65, 81.71, 81.9 (2C), 82.0 (4C), 82.1, 82.2, 82.6,
or
61.3, 61.4 (2C), 61.5 (2C), 61.6 (OMe), 66.8 (d, 2J(C,P)=11.4 Hz; C-5A or B),
83.2 (C-2, C-3, C-4C,D,E,F,G), 85.3 (d, 3J
(C,P)=9.9 Hz; C-4A
B), 89.1
or
70.7 (2C), 70.99, 71.03 (2C), 71.27, 71.32 (2C), 71.6, 71.7 (C-5C,D,E,F,G
,
(C-4B
A), 97.6, 98.1, 98.20, 98.24, 98.3, 98.7, 99.7 (C-1), 128.8 (d,
or
C-6C,D,E,F,G), 73.3 (d, 2J
(C,P)=38.9 Hz; C-5B A), 78.1, 79.3, 79.9, 80.5,
3J
131.7 ppm (d, 1J
ACHTUNGTRENNUNG
N
ACHTUNGTRNE(NUNG C,P)=8.5 Hz; o-C), 131.3 (p-C),
81.08 (C-4C,D,E,F,G), 81.10 (2C), 81.8 (2C), 82.0 (3C), 82.1 (3C), 82.3 (2C),
83.7 (2C) (C-2, C-3), 86.1 (C-4A or B), 88.9 (C-4B or A), 98.4, 98.5 (2C), 98.7,
for C67H114BO33P·EtOH (1489.39 + 46.06): C 53.97, H 7.88; found: C
53.83, H 8.00; MS (ESI-TOF): m/z (%): 1527.67 (25) [M + K]+, 1511.70
(70) [M + Na]+.
98.9, 99.1, 99.7 (C-1), 128.4 (d, 3J
(d, 2J(C,P)=18.7 Hz; o-C), 140.6 ppm (d, 1J
ACHTUNGTRENNUNG ACHTUNGTRENNUNG
31P{1H} NMR (121.5 MHz, CDCl3): d=À15.1 ppm (s); elemental analysis
calcd (%) for C67H111O33P·2CH2Cl2: (1475.55 + 169.86): C 50.37, H 7.07;
found: C 50.28, H 7.21; MS (ESI-TOF): m/z (%): 1497.7 [M + Na]+.
6A,6B,6D,6E-Tetradeoxy-6A,6B:6D,6E-bis
(epithio)-2A,2B,2C,2D,2E,2F,2G,-
ACHTUNGTRENNUNG
3A,3B,3C,3D,3E,3F,3G,6C,6F,6G-heptadeca-O-methyl-b-cyclodextrin (15):
A
solution of tetramesylate 9 (0.150 g, 0.089 mmol) in degassed acetone
(5 mL) was treated with [18]crown-6 (0.141 g, 0.534 mmol) followed by
powdered hydrated sodium sulfide (Na2S·9H2O; 0.064 g, 0.267 mmol).
After 12 h stirring at room temperature, the reaction mixture was evapo-
rated to dryness and the residue was dissolved in saturated aqueous KCl
(30 mL) and extracted with CH2Cl2 (3ꢆ30 mL). The combined organic
layers were dried (MgSO4) before removing the solvent. The crude prod-
uct was purified by column chromatography (SiO2; CH2Cl2/MeOH, 97:3,
v/v) to give the desired product 15 (0.061 g, 50%) as a white solid. Rf =
6A,6B-Dideoxy-6A,6B-(S)-phenyloxophosphinidene-2A,2B,2C,2D,2E,2F,2G,-
3A,3B,3C,3D,3E,3F,3G,6C,6D,6E,6F,6G-nonadeca-O-methyl-b-cyclodextrin (13):
The phosphane oxide 13 was obtained by bubbling air through a solution
of 12 in MeOH for 1 h at room temperature. Removal of the solvent in
vacuo gave analytically pure 13 as a white solid. Rf =0.30 (SiO2; CH2Cl2/
MeOH, 98:2, v/v); m.p. 2018C; 1H NMR (300.1 MHz, CDCl3, 258C): d
(assignment by COSY)=1.93 (t, 2J(H-6a,H-6b)=2J
(H-6a,P)=13.2 Hz,
or
1H; H-6aA
B), 2.15 (t, 2J(H-6a,H-6b)=2J(H-6a,P)=16.4 Hz, 1H;
or
1
H-6aB A), 2.90–3.03 (m, 2H; H-6bA,B), 3.11 (s, 3H; OMe), 3.13 (s, 3H;
OMe), 3.19–3.94 (m, 36H; H-2, H-3, H-4, H-5C,D,E,F,G, H-6C,D,E,F,G), 3.35 (s,
6H; OMe), 3.37 (s, 3H; OMe), 3.41 (s, 3H; OMe), 3.44 (s, 9H; OMe),
3.46 (s, 3H; OMe), 3.47 (s, 3H; OMe), 3.50 (s, 3H; OMe), 3.55 (s, 3H;
0.42 (SiO2; CH2Cl2/MeOH, 92:8, v/v); m.p. 2038C; H NMR (500.1 MHz,
CDCl3, 258C): d (assignment by COSY, TOCSY and ROESY)=2.66 (m,
2H; H-6aB,E), 2.79 (d, 2J(H-6a,H-6b)=16.6 Hz, 2H; H-6aA,D), 3.13 (m,
3
3
2H; H-2A,D), 3.17 (dd, J
2G), 3.19 (dd, 3J
(dd, 3J(H-2,H-3)=9.5 Hz, 3J
ACHTUNGTRENNUNG
G
ACHTUNGERTN(NUNG H-1,H-2)=3.6 Hz, 1H; H-
OMe), 3.58 (s, 3H; OMe), 3.61 (s, 9H; OMe), 3.62 (s, 3H; OMe), 3.63 (s,
E
ACHTUNGTRENNUNG
3
3H; OMe), 4.38 (m, 1H; H-5A or B), 4.62 (m, 1H; H-5B or A), 4.90 (d, J
G
U
1,H-2)=3.6 Hz, 1H; H-1), 4.94 (d, 3J
G
6b,H-6a)=16.6 Hz, 2H; H-6bB,E), 3.36–3.64 (m, 21H; H-2A,D, H-3, H-4,
H-6aC,F,G, H-6bA,D), 3.38 (s, 3H; OMe-6G), 3.39 (s, 6H; OMe-6C,F), 3.47 (s,
3H; OMe-2G), 3.48 (s, 3H; OMe-2C), 3.49 (s, 3H; OMe-2F), 3.50 (s, 3H;
OMe-2A), 3.51 (s, 3H; OMe-2D), 3.54 (s, 6H; OMe-2B,E), 3.58 (s, 3H;
OMe-3), 3.59 (s, 3H; OMe-3), 3.61 (s, 6H; OMe-3), 3.62 (s, 3H; OMe-3),
3
(d, J
N
G
1), 5.06 (d, 3J
N
ACHTUNGTRENNUNG
1H; H-1), 5.12 (d, 3J
ACHTUNGTRENNUNG(H-1,H-2)=3.6 Hz, 1H; H-1), 7.41–7.49 (m, 3H; m-
H, p-H), 7.64 ppm (m, 2H; o-H); 13C{1H} NMR (75.5 MHz, CDCl3,
258C): d (assignment by HMQC)=33.4 (d, 1J
(C,P)=68.0 Hz; C-6A B),
3.64 (s, 6H; OMe-3), 3.69 (dd, 2J(H-6b,H-6a)=10.3 Hz, 3J
ACHTNUGETRNNU(G H-6b,H-5)=
or
1
38.2 (d, J
N
3.8 Hz, 1H; H-6bC), 3.77–3.82 (m, 3H; H-6bF,G, H-5G), 3.87–3.89 (m, 2H;
H-5C,F), 4.06–4.12 (m, 2H; H-5A,D), 4.16–4.24 (m, 2H; H-5B,E), 4.93 (d,
58.8 (2C), 59.0 (3C), 61.2, 61.4, 61.5, 61.6 (2C), 61.7, 61.9 (OMe), 63.2
or
(d, 2J
G
3J
(H-1,H-2)=3.4 Hz, 1H; H-1C), 4.97 (d, 3J
ACHUTGTNRENNUG CAHTUNGTRENNUNG
(3C) (C-5C,D,E,F,G, C-6C,D,E,F,G), 77.3, 78.7, 79.8, 80.5, 80.6, 81.0, 81.4, 81.5,
H-1F), 5.01 (d, J
AHCTUNGTRENNUNG
3
Chem. Eur. J. 2011, 17, 3911 – 3921
ꢂ 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemeurj.org
3919

D. Armspach, D. Matt et al.
5.17 ppm (d, 3J
G
2J(H-6b,H-6a)=10.1 Hz, 3J
3J(H-1,H-2)=3.7 Hz, 1H, H-1C), 4.87 (dd, 2J(H-6b,H-6a)=12.3 Hz, 3J
6b,H-5)=1.7 Hz, 1H; H-6bE), 4.95 (d, 3J(H-1,H-2)=3.7 Hz, 1H; H-1F),
4.97 (dd, 2J(H-6b,H-6a)=12.3 Hz, 3J(H-6b,H-5)=1.2 Hz, 1H; H-6bB),
5.05 (d, 3J(H-1,H-2)=3.1 Hz, 1H; H-1D), 5.06 (d, 3J
(H-1,H-2)=3.1 Hz,
1H; H-1A), 5.08 (d, 3J(H-1,H-2)=3.3 Hz, 1H; H-1G), 5.14 (d, 3J
(H-1,H-
2)=4.1 Hz, 1H; H-1E), 5.16 ppm (d, 3J(H-1,H-2)=4.1 Hz, 1H; H-1B);
ACHTUNGTRENNUNG
CDCl3, 258C): d (assignment by HMQC)=30.9 (br s, 2C; C-6B,E), 35.4
(br s, 2C; C-6A,D), 58.1, 58.3, 58.4 (2C), 58.5, 58.6, 59.0 (2C), 59.1, 59.2 ,
61.3 (2C), 61.5 (3C), 61.6 (2C) (OMe), 70.7 (3C; C-5C,F,G), 71.1 (3C; C-
6C,F,G), 73.5 (2C; C-5B,E), 79.0 (2C; C-5A,D), 80.7, 81.0 (2C), 81.2, 81.3,
81.76 (2C), 81.81 (3C), 81.83 (3C), 82.0 (2C), 82.1, 82.2, 83.5, 84.0, 84.6,
84.7 (C-2, C-3, C-4), 97.8, 98.0, 98.8 (2C), 99.0, 99.3, 99.5 ppm (C-1); ele-
mental analysis calcd (%) for C59H100O31S2 (1369.54): C 51.74, H 7.36;
found: C 51.56, H 7.59; MS (ESI-TOF): m/z (%): 1391.56 (100) [M +
Na]+.
G
ACHTUNGTRENNUNG
AHCTUNGTRENNUNG
AHCTUNGTRENNUNG
N
ACHTUNGTRENNUNG
G
ACHTUNGTRENNUNG
AHCTUNGTRENNUNG
13C{1H} NMR (75.5 MHz CDCl3, 258C): d (assignment by HMQC)=58.2
(3C), 58.5, 58.98, 59.03, 59.1 (3C), 59.4, 61.1, 61.2, 61.3, 61.5, 61.8 (3C)
(OMe), 68.4 (3C), 68.6 (C-5A,D,B,E), 70.6 (2C), 70.89 (C-6C,F,G), 70.89, 71.2,
71.3 (C-5C,F,G), 73.8 (3C), 73.9 (C-6A,D,B,E), 80.0, 80.7, 81.2, 81.3 (3C), 81.5
(6C), 81.6, 81.65, 81.70, 81.8 (3C), 82.6, 82.8, 82.9 (C-2, C-3, C-4), 97.9,
98.9, 99.1, 99.7 (2C), 100.4, 100.5 ppm (C-1); elemental analysis calcd
(%) for C59H100O39S2: (1497.53): C 47.32, H 6.73, found: C 47.55, H 6.67;
MS (ESI-TOF): m/z (%): 1519.52 (100) [M + Na]+.
ACTHNUTRGNEUNG
6A,6B,6D,6E-Tetradeoxy-6A,6B:6D,6E-bis(sulfate)-2A,2B,2C,2D,2E,2F,-
3A,3B,3C,3D,3E,3F,6C,6F-tetradeca-O-methyl-a-cyclodextrin (18): A solution
of freshly distilled thionyl chloride (0.72 g, 0.44 mL, 6.08 mmol) in
CH2Cl2 (25 mL) was added dropwise to a solution of tetrol 17 (1.57 g,
1.35 mmol) and NEt3 (0.68 g, 0.93 mL, 6.75 mmol) in CH2Cl2 (300 mL) at
À788C. The reaction mixture was stirred for 1 h at À788C whereupon it
was allowed to reach 08C, quenched with saturated aqueous NaHCO3
(200 mL), and extracted with CHCl3 (3ꢆ150 mL). The combined organic
extracts were dried (MgSO4) before being evaporated to dryness to
afford a colourless residue, which was dissolved in a mixture of CH2Cl2
(18 mL), MeCN (18 mL) and water (36 mL). Ruthenium trichloride
(6 mg, 28ꢆ10À3 mmol) and sodium periodate (0.64 g, 2.97 mmol) were
then added and the reaction mixture was stirred for 12 h at room temper-
ature before adding saturated aqueous NaHCO3 (200 mL). Subsequent
extraction with CHCl3 (3ꢆ100 mL) was followed by drying of the organic
extracts (MgSO4). Removal of the solvent in vacuo gave a colourless resi-
due, which was subjected to column chromatography (SiO2; CH2Cl2/
MeOH, 97:3, v/v) to afford 18 (1.66 g, 95%) as a colourless solid. Rf =
0.51 (SiO2; CH2Cl2/MeOH, 90:10, v/v); m.p. 1898C; 1H NMR
X-ray crystallographic data of 4: Single crystals were obtained by slow
diffusion of pentane into a commercial ethyl acetate solution of 4.
C71H116B2O31P2·0.5
clinic; P21; a=13.1531(2), b=21.8818(3), c=16.5539(2) ꢄ, b=
104.303(1)8; V=4616.75(11) ꢄ3; Z=2; 1calcd =1.179 MgmÀ3; l
(MoKa)=
0.71073 ꢄ; m=0.123 mmÀ1; F
(000)=1760; T=150 K. The sample (0.35ꢆ
ACTHGNUTRNEU(NGN C4H8O2)·0.5AHCNUTTRGEN(GNUN C5H12)·0.5CAHTNUGRTEN(NUNG H2O); MG =1638.33; mono-
ACHTUNGTRENNUNG
AHCTUNGTRENNUNG
0.35ꢆ0.32 mm) was studied with an Oxford Diffraction Xcalibur Saphir 3
CCD with graphite monochromatised MoKa radiation. The structure was
solved with SIR-97,[34] which revealed the non-hydrogen atoms of the
molecule. After anisotropic refinement, many hydrogen atoms were
found with a Fourier difference analysis. The whole structure was refined
with SHELX-97[35] and full-matrix least-square techniques. Use of F2
magnitude; x, y, z, bij for C, B, O, P atoms, x, y, z, in riding mode for H
atoms; 1033 variables and 15406 observations with I> 2.0s(I); calcd w=
2
2
2
2(Fo ) + (0.0840 P)2] where P=(Fo + 2 Fo )/3 with the resulting R=
1/[s ACHTGNURTENNUGN
(300.1 MHz, CDCl3, 258C): d (assignment by COSY)=3.07 (t, 3J
3)=3J(H-4,H-5)=9.4 Hz, 2H; H-4A,D or B,E), 3.13–3.21 (m, 6H; H-2), 3.28
ACHTUNGTRENNUNG
(t, 3J(H-4,H-3)=3J(H-4, H-5)=9.4 Hz, 2H; H-4B,E A,D), 3.38 (s, 6H;
0.0475, Rw =0.1241, and Sw =0.954; D1 <0.592 eꢄÀ3. Flack parameter:
ACHTUNGTRENNUNG
0.02(6).
G
OMe), 3.48 (s, 12H; OMe), 3.54 (s, 6H; OMe), 3.61 (s, 6H; OMe), 3.65
X-ray crystallographic data of 18: Single crystals of 18 were obtained by
slow diffusion of pentane into a dichloromethane solution of the com-
(s, 6H; OMe), 3.66 (s, 6H; OMe), 3.42–3.60 (m, 8H; H-3B,E or A,D and C,F, H-
or
4C,F, H-6bC,F), 3.89–3.91 (m, 4H; H-3A,D B,E, H-5C,F), 4.01–4.09 (4H; H-
pound. C50H84O34S2·2
a=14.6490(2), b=16.4157(2), c=16.0156(2) ꢄ, b=109.185(1)8; V=
3637.43(8) ꢄ3; Z=2; 1calcd =1.369 MgmÀ3
(MoKa)=0.71073 ꢄ; m=
0.306 mmÀ1; F
(000)=1586; T=150 K. The sample (0.26ꢆ0.22ꢆ0.22 mm)
CAHTUTNGERNN(GU CH2Cl2)·0.5AHCTUNTGRENN(UGN C5H12); MG =1499.22; monoclinic; P21;
3
3
6bA,D or B,E, H-6aC,F), 4.17 (dd, J
G
E
H-5B,E A,D), 4.37 (d, 2J(H-6b,H-6a)=9.8 Hz, 2H, H-6bB,E A,D), 4.52 (t,
or
or
;
lACHTUNGTRENNUNG
3J
G
(H-5,H-6b)=10.2 Hz, 2H; H-5A,D B,E), 4.69 (dd, 2J(H-
AHCTUNGTRENNUNG
6a,H-6b)=9.8, 3J
N
was studied with an Oxford Diffraction Xcalibur Saphir 3 CCD with
graphite monochromatised MoKa radiation. The structure was solved with
SIR-97,[34] which revealed the non-hydrogen atoms of the molecule. After
anisotropic refinement, many hydrogen atoms were found with a Fourier
difference analysis. The whole structure was refined with SHELX-97[35]
and full-matrix least-square techniques. Use of F2 magnitude; x, y, z, bij
1,H-2)=3.2 Hz, 2H; H-1), 4.98 (overlapping d, 2H; H-6aA,D B,E), 5.01
3
(d, J
(H-1,H-2)=3.2 Hz, 2H; H-1), 5.08 (d, 3J
1) ppm; 13C{1H} NMR (75.5 MHz, CDCl3, 258C):
HMQC)=57.7, 58.0, 58.7, 59.2, 61.6, 61.95, 62.00 (OMe), 67.4 (C-5A,D or B,E),
69.1 (C-5B,E A,D), 70.9 (C-6C,F), 71.4 (C-5C,F), 73.0 (C-6A,D B,E), 75.0
or
(C-6B,E A,D), 80.9, 81.2 (2C), 81.4, 81.5, 82.3 (2C), 83.6, 86.8 (C-2, C-3,
or
for C, O, S atoms, x, y, z, in riding mode for H atoms; 874 variables and
2
11936 observations with I> 2.0s(I); calcd w=1/[s
2(Fo ) + (0.1186 P)2]
C-4), 98.3, 100.3, 100.6 ppm (C-1); elemental analysis calcd (%) for
2
2
C50H84O34S2·0.5CHCl3: (1293.31
+ 59.69): C 44.83, H 6.29; found: C
where P=(Fo + 2 Fo )/3 with the resulting R=0.0506, Rw =0.1476, and
44.91, H 6.37; MS (ESI-TOF): m/z (%): 1315.42 (100) [M + Na]+.
Sw =0.842; D1 <1.306 eꢄÀ3. Flack parameter: 0.00(5).
ACTHNUTRGNEUNG
6A,6B,6D,6E-Tetradeoxy-6A,6B:6D,6E-bis(sulfate)-2A,2B,2C,2D,2E,2F,2G-
CCDC-744760 (4) and 738543 (18) contain the supplementary crystallo-
graphic data for this report. These data can be obtained free of charge
from The Cambridge Christallographic Data Centre via www.ccdc.cam.
ac.uk/data_request/cif.
3A,3B,3C,3D,3E,3F,3G,6C,6F,6G-heptadeca-O-methyl-b-cyclodextrin (19): Pre-
pared from 8 (1.28 g, 0.93 mmol) according to the above procedure
(1.34 g, 95%). Rf =0.51 (SiO2; CH2Cl2/MeOH, 90:10, v/v); m.p. 1918C;
1H NMR (600.1 MHz, CDCl3, 258C): d (assignment by COSY, TOCSY
3
and ROESY)=3.11–3.21 (m, 7H; H-2A,C,D,F,G, H-4B,E), 3.26 (dd, J
G
3)=9.1 Hz, 3J
8.6 Hz, 3J
N
ACHTUNGTRENUN(NG H-2,H-3)=
ACHTUNGTRENNUNG
Acknowledgements
The authors are grateful to the CNRS, the Rꢀgion Alsace, and the
French Agence Nationale de la Recherche (ANR Watercat) for financial
support.
4C, H-5C,F,G), 3.86 (dd, 2J(H-6b,H-6a)=10.9 Hz, 3J
1H; H-6bF), 3.94 (dd, 2J(H-6b,H-6a)=11.1 Hz, 3J
AHCTUNGTRENNUNG
ACHTUNGTRENNUNG
1H; H-6bG), 3.98 (d, 2J(H-6b,H-6a)=11.1 Hz, 1H, H-6bC), 4.13–4.18 (m,
3H; H-5A,D, H-6aB), 4.24 (m, 1H; H-6aE), 4.33 (td, 3J
5,H-6a)=10.0 Hz, 3J(H-5,H-6b)=1.1 Hz, 1H; H-5B), 4.41 (td, 3J
(H-5,H-6b)=1.4 Hz, 1H; H-5E), 4.45 (dd,
(H-6a,H-5)=1.0 Hz, 1H; H-6aA), 4.50 (dd,
(H-6a,H-5)=1.0 Hz, 1H; H-6aD), 4.58 (dd,
(H-6b,H-5)=4.2 Hz, 1H; H-6bD), 4.61 (dd,
G
E
[1] M. Sollogoub, Eur. J. Org. Chem. 2009, 1295–1303.
[2] G. Wenz, Angew. Chem. 1994, 106, 851–870; Angew. Chem. Int. Ed.
Engl. 1994, 33, 803–822.
[3] D. Armspach, D. Matt, L. Toupet, Angew. Chem. 2009, 121, 4625–
4628; Angew. Chem. Int. Ed. 2009, 48, 4555–4558.
E
ACHTUNGTRENNUNG
4)=3J(H-5,H-6a)=9.9 Hz, 3J
ACHTUNGTRENNUNG ACHTUNGTRENNUNG
2J(H-6a,H-6b)=10.1 Hz, 3J
2J(H-6a,H-6b)=10.1 Hz, 3J
AHCTUNGTRENNUNG
A
2J(H-6b,H-6a)=10.1 Hz, 3J
C
[4] R. Breslow, S. Dong, Chem. Rev. 1998, 98, 1997–2011.
3920
www.chemeurj.org
ꢂ 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2011, 17, 3911 – 3921

Capping Cyclodextrin
FULL PAPER
[5] C. Jeunesse, D. Armspach, D. Matt, Chem. Commun. 2005, 5603–
5614.
[22] This reaction also produced a-CDs bearing dangling “bis-trityl”
units. These results will be published elsewhere.
[23] E. Engeldinger, L. Poorters, D. Armspach, D. Matt, L. Toupet,
Chem. Commun. 2004, 634–635.
[24] L. Poorters, D. Armspach, D. Matt, L. Toupet, S. Choua, P. Turek,
Chem. Eur. J. 2007, 13, 9448–9461.
[25] B. Benmerad, P. Clair, D. Armspach, D. Matt, F. Balegroune, L.
Toupet, Chem. Commun. 2006, 2678–2680.
[26] D. Armspach, L. Poorters, D. Matt, B. Benmerad, P. Jones, I. Dix, L.
Toupet, J. Inclusion Phenom. Macrocyclic Chem. 2007, 57, 243–250.
[27] L. Poorters, M. Lejeune, D. Armspach, D. Matt, Actual. Chim. 2009,
15–18.
[6] D. Armspach, D. Matt, C. R. Chimie 2011, 14, 135–148.
[7] M. T. Reetz, S. R. Waldvogel, Angew. Chem. 1997, 109, 870–873;
Angew. Chem. Int. Ed. Engl. 1997, 36, 865–867.
[8] A. R. Khan, P. Forgo, K. J. Stine, V. T. D’Souza, Chem. Rev. 1998,
98, 1977–1996.
[9] T. Lecourt, A. Herault, A. J. Pearce, M. Sollogoub, P. Sinaꢇ, Chem.
Eur. J. 2004, 10, 2960–2971.
[10] G. K. Rawal, S. Rani, S. Ward, C.-C. Ling, Org. Biomol. Chem. 2010,
8, 171–180.
[11] O. Bistri, P. Sinaꢇ, J. J. Barbero, M. Sollogoub, Chem. Eur. J. 2007,
13, 9757–9774.
[12] G. K. Rawal, S. Rani, C.-C. Ling, Tetrahedron Lett. 2009, 50, 4633–
4636.
[13] X. Luo, Y. Chen, G. Huber, Y. Zhang, P. Sinaꢇ, C. R. Chim. 2004, 7,
25–28.
[14] S. Xiao, M. Yang, P. Sinaꢇ, Y. Blꢀriot, M. Sollogoub, Y. Zhang, Eur.
J. Org. Chem. 2010, 1510–1516.
[28] Unlike its a-CD analogue TRANSDIP, diphosphane 10 was formed
together with side products having the same molecular mass and po-
larity as 10. Careful analysis revealed the presence of a -PPhH sub-
stituent in all cases (31P NMR: d ꢀ À40 ppm).
[29] L. Poorters, D. Armspach, D. Matt, L. Toupet, Dalton Trans. 2007,
3195–3202.
[30] J.-C. Hierso, D. Armspach, D. Matt, C. R. Chim. 2009, 12, 1002–
1013.
[31] D. Armspach, D. Matt, Chem. Commun. 1999, 1073–1074.
[32] Z. Chen, J. S. Bradshaw, Y. F. Shen, Y. Habata, M. L. Lee, J. Org.
Chem. 1997, 62, 8529–8534.
[33] M. Petrillo, L. Marinescu, C. Rousseau, M. Bols, Org. Lett. 2009, 11,
1983–1985.
[34] A. Altomare, M. C. Burla, M. Camalli, G. Cascarano, C. Giacovaz-
zo, A. Guagliardi, A. G. G. Moliterni, G. Polidori, R. Spagna, J.
Appl. Crystallogr. 1998, 31, 74–77.
[15] C.-C. Ling, A. W. Coleman, M. Miocque, Carbohydr. Res. 1992, 223,
287–291.
[16] S. Ward, P. Zhang, C.-C. Ling, Carbohydr. Res. 2009, 344, 808–814.
[17] a) L. Poorters, D. Armspach, D. Matt, Eur. J. Org. Chem. 2003,
1377–1381; b) D. Armspach, D. Matt, Carbohydr. Res. 1998, 310,
129–133.
[18] I. Tabushi, K. Shimokawa, N. Shimizu, H. Shirakata, K. Fujita, J.
Am. Chem. Soc. 1976, 98, 7855–7856.
[19] I. Tabushi, L. C. Yuan, K. Shimokawa, K. Yokota, T. Mizutani, Y.
Kuroda, Tetrahedron Lett. 1981, 22, 2273–2276.
[20] I. Tabushi, T. Nabeshima, K. Fujita, A. Matsunaga, T. Imoto, J. Org.
Chem. 1985, 50, 2638–2643.
[21] D. Armspach, L. Poorters, D. Matt, B. Benmerad, F. Balegroune, L.
Toupet, Org. Biomol. Chem. 2005, 3, 2588–2592.
[35] G. M. Sheldrick, SHELXL-97, Program for Crystal Structure Refine-
ment University of Gçttingen, Gçttingen (Germany) 1997.
Received: September 2, 2010
Revised: November 9, 2010
Published online: March 1, 2011
Chem. Eur. J. 2011, 17, 3911 – 3921
ꢂ 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemeurj.org
3921