Phosphane-phosphite chelators built on a α-cyclodextrin scaffold: Application in rh-catalysed asymmetric hydrogenation and hydroformylation

Article abstract of DOI:10.1002/ejoc.201300854

Four hybrid phosphane-phosphite ligands were synthesised by regioselective A,B-functionalisation of a methylated α-cyclodextrin (α-CD) scaffold. In all these ligands the phosphite part comprises a 2,2′-bisaryloxyphosphanyloxy group. The ligands, which dis

Full text of DOI:10.1002/ejoc.201300854

FULL PAPER
DOI: 10.1002/ejoc.201300854
Phosphane-Phosphite Chelators Built on a α-Cyclodextrin Scaffold:
Application in Rh-Catalysed Asymmetric Hydrogenation and Hydroformylation
Matthieu Jouffroy,[a] David Sémeril,[a] Dominique Armspach,*[a] and Dominique Matt*[a]
Keywords: Cyclodextrins / Phosphane ligands / Asymmetric catalysis / Platinum / Rhodium / Cavitands
Four hybrid phosphane-phosphite ligands were synthesised
by regioselective A,B-functionalisation of a methylated α-
cyclodextrin (α-CD) scaffold. In all these ligands the phos-
phite part comprises a 2,2Ј-bisaryloxyphosphanyloxy group.
The ligands, which display inherent chirality, readily form
12-membered chelate rings with d8-metal ions. In the most
flexible chelates (those with an unsubstituted 2,2Ј-bis-
phenoxy group), the metal plane describes a fan-like motion
about the P···PЈ axis with concomitant fast atropisomerisation
of the biaryl unit. When the latter is blocked, as in the 2,2Ј-
binaphthyloxyphosphites, the fan-like motion no longer
takes place. Rhodium complexes of the CDs were assessed
in asymmetric hydrogenation of α-dehydroamino acid esters
and hydroformylation of styrene. Poor enantiodiscrimination
was observed for the highly mobile chelate complexes,
whereas the more rigid ones all resulted in significant ee val-
ues. The best performing hydrogenation catalyst is the one
in which both chiral components – CD and (S)-binaphthyl –
behave in a synergistic way.
phosphanes based on other inherently chiral macrocycles
have already been reported.[3b]
Introduction
Despite the presence of numerous stereogenic centres em-
bedded in their rigid skeleton, to date only few cyclodex-
trin (CD) derived ligands have been used in asymmetric ca-
talysis. In the corresponding metal catalysts the reaction
usually takes place outside the cavity, far from the centres
of chirality in which efficient asymmetric induction could
occur. Nevertheless, when the catalytic centre of these com-
plexes is maintained in a rigid manner with respect to the
CD backbone, significant ee values can be obtained. Such
a feature has been observed, for example, in metallocyclo-
dextrins capable of forming transient inclusion complexes in
water with prochiral substrates to be transformed.[1] Chiral-
ity transfer from the glucose units to the metal first sphere
of coordination is also often very effective when rigid che-
late complexes are obtained from CDs bearing two close
pendant arms.[2] A potential strategy for enhancing chiral
induction consists in making the CD shape inherently chiral
by anchoring a set of distinct groups on its conical back-
bone so as to produce a CD with a substitution pattern non
superimposable with its mirror image.[3] However, whether
the effects of inherent chirality will synergistically add to
those induced by the asymmetric centres of the backbone
is difficult to predict. It is worth mentioning here that di-
In this paper we describe the first inherently chiral CDs
bearing two distinct PIII substituents, namely a phosphane
unit and a phosphite one. These hybrid ligands, which are
ideal for chelate formation, have been assessed in the rho-
dium-catalysed hydrogenation of α-dehydroamino acid es-
ters and hydroformylation of styrene. Chiral phosphanyl-
phosphites constitute a class of ligands that have found
many applications in asymmetric catalytic transforma-
tions,[4] notably hydrogenation[5] and hydroformylation[6] of
prochiral olefins.
Results and Discussion
Synthesis of Phosphane-Phosphite Ligands
The synthesis of the ligands started with the deprotection
[7]
of phosphane borane adduct 1·BH3 with boiling dieth-
ylamine to give 1 quantitatively (Scheme 1). Surprisingly,
phosphorochloridites 2–5 did not react with the CD pri-
mary hydroxy groups in the presence of a tertiary amine
such as Et3N, which are the general reaction conditions
used for the formation of phosphites from secondary and
tertiary alcohols. Only the CD alkoxide obtained by re-
acting 1 with NaH in hot toluene, was sufficiently nucleo-
philic to give the corresponding phosphane-phosphite li-
gands 6–9 with isolated yields ranging from 37 to 62%.
The chemical shifts for the two phosphorus donor atoms
are typical of phosphite (146.6 Յ δ Յ 150.7 ppm) and di-
arylalkylphosphane (–21.4 Յ δ Յ –20.3 ppm) functionali-
ties. All NMR spectra displayed sharp signals at room tem-
[a] Laboratoire de Chimie Inorganique Moléculaire et Catalyse,
Institut de Chimie UMR 7177 CNRS, Université de
Strasbourg,
1, rue Blaise Pascal, 67008 Strasbourg cedex, France
E-mail: d.armspach@unistra.fr
dmatt@unistra.fr
Homepage: http://inorganics.online.fr
Supporting information for this article is available on the
WWW under http://dx.doi.org/10.1002/ejoc.201300854.
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M. Jouffroy, D. Sémeril, D. Armspach, D. Matt
FULL PAPER
Scheme 1. Synthesis of phosphane-phosphite ligands 6–9.
perature except for biphenyl derivative 7, the 31P NMR CH2Cl2 (mass spectrum showing a peak corresponding to
spectrum of which, recorded at 60 °C, showed a broad sing- the [M + Na]+ cation). It is noteworthy that chelate forma-
let for the phosphite phosphorus atom, whereas the phos- tion did not require high dilution conditions. Cationic com-
phane signal was sharp. This is likely because of fluxional plexes could also be obtained, again with no oligomeric ma-
behaviour involving the tBu-substituted biphenyl unit, terial being formed, by simply mixing the ligand with a
which is sufficiently congested to interact sterically with the metal precursor. For example, Rh complexes 11–14 were
CD platform so that slow interconversion of biphenyl oc- obtained by reacting [Rh(1,5-cyclooctadiene)2]BF4 with the
curs on the NMR time scale as previously noticed for sim- appropriate heterobidentate ligand (6–9). The NMR spec-
ilar bulky diphosphites.[8] This is obviously not the case tra of platinum complex 10, and rhodium complexes 12 and
with less sterically-demanding ligand 6 in which the same 13, are broad at room temperature. Upon raising the tem-
process is much faster, neither so for binaphthyl derivatives perature to 60 °C, all NMR spectra became sharp. The
8 and 9 in which free rotation about the aryl-aryl bond is 31P–31P coupling constants for all five complexes are typical
2
prevented. None of the ligands displayed 31P–31P through- of cis stereochemistry (23 Hz Յ JP,PЈ Յ 42 Hz).[5a] As ex-
space coupling, unlike other sugar-based phosphane-phos- pected for C1-symmetric compounds, four distinct signals
phite ligands.[9]
were detected for the vinylic protons of the coordinated
cyclooctadiene in all RhI complexes (see Experimental Sec-
tion).
Chelating Properties
As revealed by a variable-temperature (VT) NMR spec-
Despite the 10-bond separation between the two donor troscopic study, complex 10 displayed fluxional behaviour
atoms, we were delighted to find out that all CD ligands in solution. The 31P NMR spectrum, recorded in CDCl3 at
form readily chelate complexes, as could easily be deduced –60 °C,[10] revealed the presence of four species, two of them
from a combination of ESI-MS and NMR spectroscopy. having broad signals at this temperature, and the other two,
Thus, neutral PtII complex 10 (Figure 1) was obtained present in a 60:40 ratio, displayed sharp ones (see the Sup-
quantitatively by reacting a stoichiometric amount of the porting Information). Each of the latter are characterized
1
phosphane-phosphite ligand 6 with [PtCl2(PhCN)2] in by an ABX pattern [2J(AB) = 23 Hz, J(PAPt) = 3343 Hz
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Phosphane-Phosphite Chelators Built on a α-Cyclodextrin Scaffold
Figure 1. Chelate complexes obtained from heterobidentate ligands 6–9.
Figure 2. Two energy-minimized conformers of 10 (SPARTAN) that are consistent with the ROESY spectrum, which revealed cross-
peaks between ortho aromatic protons of both phenyl rings of the PPh2 unit and the same H-4A proton (distances given).
and 1J(PBPt) = 5878 Hz (major species) and 2J(AB) = taining complexes atropoisomerisation is blocked, so that
1
1
23 Hz, J(PAPt) = 3364 Hz and J(PBPt) = 5965 Hz (minor the only possible motion is the fanning motion of the che-
[10]
species)] indicative of cis complexes. Upon raising the tem- late ring. Both 31P NMR spectra recorded in CDCl3 re-
perature, the signals first broadened, then coalesced near mained sharp upon cooling the samples to –60 °C suggest-
–30 °C, and finally merged at 60 °C into a single ABX spec- ing that a single conformer was present in both cases. Care-
trum [2J(AB) = 23 Hz, 1J(PAPt) = 3408 and 1J(PBPt) = ful analysis of the 2D ROESY spectrum of 14 revealed that
6136 Hz]. The best way to rationalise the observed data is here the H-4A atom correlates with the ortho protons of
to consider two different motions. One of them involves in- only one P-phenyl ring unlike that of 10 in which two cross-
terconversion of the sterically unhindered biphenyl unit, peaks were observed. This confirms that only one con-
whereas the second one is related to a fan-like movement former of 14 is present in solution, but its identification
of the P2PtCl2 plane about the PA···PB axle. Confirmation (“in” or “out” form) was not achieved.[11] Clearly, the na-
of the flexibility of the rather large chelate ring came from ture of the biaryl unit has a deep impact on the mobility of
a ROESY experiment at 60 °C, which showed that 10 gave the chelate ring.
rise to cross-peaks originating from through-space corre-
lations between the outer-cavity H-4A proton and ortho aro-
matic protons of both phenyl rings of the PPh2 unit. SPAR-
TAN calculations produced two energy-minimized con-
Catalytic Studies
formers, one of them having its P2PtCl2 unit oriented
Five different α-dehydroamino esters 15–19 were used to
towards the centre of the cavity, the other being clearly lo- assess the performance of complexes 11–14 in asymmetric
cated outside (Figure 2). In keeping with the observed catalysis (Scheme 2). As shown in Table 1, all phosphane-
NMR spectroscopic data, the phenyl ring that comes close phosphite Rh complexes promoted olefin hydrogenation
to the CD is different in each conformer. The calculations with reasonable reaction rates at 5 bar of H2 at room tem-
also revealed that in the “in” and “out” conformers the bis- perature. Not surprisingly the presence of bulky tert-butyl
aryl moieties have opposite configurations.
groups in 7 slowed down the reaction to a certain extent
VT 31P NMR spectroscopic studies were also performed (Table 1, Entries 6–10). However, as noticed previously by
for rhodium complexes 13 and 14. In these binaphthyl-con- van Leeuwen[12] and Ruiz,[9] these groups are extremely
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M. Jouffroy, D. Sémeril, D. Armspach, D. Matt
FULL PAPER
beneficial for efficient asymmetric induction. Ligand 7 is no Table 1. Enantioselective hydrogenation of α-dehydroamino esters
with phosphane-phosphite complexes 11–14.[a]
exception and led to significantly higher ee values than
those obtained with much more flexible 6 (4.5 fold increase
on average depending on the substrate used). The fact that
modification of this particular unit produced dramatic
changes in the enantioselectivity indicates that the phos-
phite unit is predominantly responsible for enantiodiscrim-
ination. Without the presence of stereogenic biaryl units,
the formation of the (R) enantiomer was always favoured
regardless of the substrate used. It is clear that the chirality
of the cyclodextrin platform is somehow transferred to the
chelate ring, but the question whether enantiodiscrimin-
ation is caused by the inherent chirality of the CD platform
and/or by a particular conformation of the metallocycle re-
Conv. [%] ee [%]
Entry
Complex
R
Config.
[b]
[c]
1
2
3
4
5
6
7
8
11
Ph
100
100
100
100
100
73
95
62
97
16
100
100
100
100
100
100
100
100
100
100
8
14
8
S
R
R
R
R
R
R
R
R
R
S
S
S
S
S
R
R
R
R
R
4-F-C6H4
4-Cl-C6H4
3,4-Cl2-C6H3
2-naphthyl
Ph
4-F-C6H4
4-Cl-C6H4
3,4-Cl2-C6H3
2-naphthyl
Ph
4-F-C6H4
4-Cl-C6H4
3,4-Cl2-C6H3
2-naphthyl
Ph
4-F-C6H4
4-Cl-C6H4
3,4-Cl2-C6H3
2-naphthyl
12
10
60
48
56
34
52
24
46
34
24
70
58
58
62
52
92
12
13
14
9
10
11
12
mains open. Interestingly, a permethylated 6A,6B-diphos- 13
phanyl-β-CD reported by Wong et al.[2b] produced enantio-
selectivities similar to those obtained with catalyst 12 in the
asymmetric hydrogenation of 15 (Table 1, Entry 6).
14
15
16
17
18
19
20
A clear match/mismatch relationship was observed upon
introducing a stereogenic binaphthyl unit into the phos-
phite-coordinating unit. Whereas (S)-binaphthyl-based cat-
alyst 14 led to a significant increase in the amount of (R)-
enantiomer being produced, reaching 92% for bulky
naphthyl-containing substrate 19 (Table 1, Entry 20), the
presence of (R)-binaphthyl counterpart 13 reversed the
sense of enantiodiscrimination [formation of the (S)-prod-
uct], and led to significantly lower ee values (Table 1, En-
tries 11–15,). Clearly, the introduction of a (S)-binaphthyl
[a] General conditions: P(H2) = 5 bar, T = 25 °C, 24 h; [substrate/
complex = 100:1]. [b] Conversions were determined by means of
1H NMR spectroscopic analysis. [c] Enantioselectivities were deter-
mined by chiral GC analysis with a CHROMPAK chiral fused sil-
ica 25 mϫ0.25 mm. Coating Chirasil-l-Val column.
moiety enhances the enantiodiscrimination brought about
by the CD skeleton. We further observed a significant ee
increase upon lowering the H2 pressure to 1 bar (Table 2,
Entry 3).
Ligand 7 was also assessed in the asymmetric hydroform-
ylation of styrene (Table 3). The linear and branched alde-
hydes were formed in a standard l:b ratio of 0.3. Relative
to other phosphane-phosphite ligands, the activity of the
catalyst is above average and the observed enantioselecti-
vities, despite being moderate [up to 50% ee in favour of
the (R)-product], are similar to those obtained with the best
performing sugar-based phosphane-phosphites.[6,13]
Scheme 2. Rhodium-catalysed asymmetric hydrogenation of α-de-
hydroamino esters.
Table 2. Optimization of the catalytic hydrogenation of 17 with best-performing complex 14.
Entry
T [°C]
P(H2)
Time [h]
Charge [mol-%]
Conversion [%][a]
ee [%][b]
Configuration
1
2
3
4
25
0
25
25
5
5
1
5
24
4
24
24
1
1
1
100
63
100
75
62
60
75
71
R
R
R
R
0.25
[a] Conversions were determined by means of 1H NMR spectroscopic analysis. [b] Enantioselectivities were determined by chiral GC
analysis with a CHROMPAK chiral fused silica 25mϫ0.25 mm. Coating Chirasil-l-Val column.
Table 3. Rhodium-catalyzed hydroformylation of styrene.[a]
Entry
Complex
Conversion [%][b] (time [h])
TOF[c]
Aldehydes[b] l [%] b [%]
l/b[d]
ee (%)[b]
1
2
12
12
59.8 (4)
Ͼ99 (7)
374
104
24.2 75.8
23.8 76.2
0.3
0.3
50
50
[a] Styrene (5 mmol), styrene/complex = 2500, P(CO/H2) = 20 bar, T = 80 °C, toluene/n-decane (15 mL/0.5 mL), incubation overnight at
80 °C under P(CO/H2) = 20 bar. [b] Determined by GC analysis with decane as internal standard. [c] Mol(converted styrene) mol(Rh)
–1h–1. [d] l:b aldehyde ratio.
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Phosphane-Phosphite Chelators Built on a α-Cyclodextrin Scaffold
Conclusion
Access to the first C1-symmetric heterobidentate ligands
built on a cavity-shaped molecule was made possible by
proximally functionalising a methylated α-CD with two dif-
ferent coordinating groups. Despite the large separation be-
tween the two donor atoms, all the phosphane-phosphite
ligands proved to be sufficiently preorganized to form
quantitatively both neutral PtII and cationic RhI chelate
complexes. As shown by extensive NMR spectroscopic
studies, chelate comlex 10 undergoes two motions in solu-
tion, one being associated with atropoisomerisation of the
biphenyl unit, the other being a fan-like movement of the
metallocyclic unit about the PA···PB axle, which displaces
the metal centre from above the cavity to its exterior. Such
motions are impeded in binaphthyl complexes 13 and 14.
Poor enantiodiscrimination was observed by using 11 in the
asymmetric hydrogenation of α-dehydroamino acid esters.
On the contrary, more rigid complexes 12–14 all resulted in
significant ee values, with the best performing system (14)
being the one in which both chiral components – CD and
(S)-binaphthyl – behave in a synergistic way. Even higher ee
values are expected with analogues having bulkier biaryl
units, which are likely to enhance the inherently chiral prop-
erties of the C1-symmetric CD platform.
6A-Deoxy-6A-diphenylphosphanyl-2A,2B,2C,2D,2E,2F,3A,3B,3C,
3D,3E,3F,6C,6D,6E,6F-hexadeca-O-methyl-α-cyclodextrin (1): A solu-
tion of 1·BH3 (1.258 g, 0.91 mmol) in degassed Et2NH (20 mL) was
heated to reflux for 12 h. After cooling to room temperature, the
reaction mixture was evaporated to dryness. The residue was then
taken up in toluene and the resulting suspension filtered through a
pad of Celite. Removal of the solvent in vacuo afforded analytically
pure 1 (1.241 g, 99 %) as a colourless solid. Rf (SiO2, CH2Cl2/
MeOH, 90:10, v/v) = 0.64, m.p. dec. 1H NMR (400.1 MHz, CDCl3,
25 °C): δ = [assignment by combined COSY and heteronuclear sin-
gle quantum coherence (HSQC)] = 1.49 (m, 1 H, OHB), 2.60 (ddd,
2
3
2J6a-H,6b-H = 15.6, J6b-H,P = 2.6, J6a-H,5-H = 5.9 Hz, 1 H, 6aA-H),
2.70 (td, 2J6a-H,6b-H = 15.6, 2J6b-H,P = 3J6b-H,5-H = 3.9 Hz, 1 H, 6bA-
3
3
H), 3.06 (dd, J2-H,3-H = 9.2, J2-H,1-H = 3.0 Hz, 1 H, 2-H), 3.08 (s,
3 H, OMe), 3.12–3.20 (5 H, 2-H), 3.21 (m, 1 H, 6-H), 3.39 (s, 3 H,
OMe), 3.40 (s, 3 H, OMe), 3.43 (s, 3 H, OMe), 3.47 (s, 3 H, OMe),
3.48 (s, 9 H, OMe), 3.49 (s, 3 H, OMe), 3.50 (s, 3 H, OMe), 3.62
(s, 3 H, OMe), 3.63 (s, 9 H, OMe), 3.64 (s, 3 H, OMe), 3.66 (s, 3
H, OMe), 3.37–3.92 (26 H, 3-H, 4-H, 5-H, 6-H), 4.18 (m, 1 H, 5A-
3
H), 4.91 (d, J1-H,2-H = 3.2 Hz, 1 H, 1-H), 5.00–5.03 (2 H, 1-H),
5.04–5.07 (3 H, 1-H), 7.14–7.19 (2 H, p-H), 7.22–7.33 (4 H, m-
H), 7.39–7.48 (4 H, o-H) ppm. 13C{1H} NMR (100.6 MHz, CDCl3,
1
25 °C): δ = (assignment by HSQC) = 31.83 (d, JC,P = 18.3 Hz, C-
6A), 57.77, 57.91, 57.93, 58.16, 58.89, 59.12 [ϫ 5] (OMe), 61.41 (C-
6B), 61.66, 61.76, 61.86, 61.91 [ϫ 3] (OMe), 70.79, 70.92, 71.05 (C-
5), 71.09, 71.19 (C-6), 71.35, 71.45 (C-5), 71.52 [ϫ 2] (C-6), 72.14
(C-5), 81.11, 81.21, 81.24, 81.28, 81.33 [ϫ 2], 81.78, 81.97, 82.06,
82.14, 82.17 [ϫ 2], 82.31 [ϫ 2], 82.36, 82.48 [ϫ 2] (C-2, C-3, C-4),
87.14 (d, 3JC,P = 11.6 Hz, C-4A), 99.32, 99.85, 99.93, 100.07, 100.22,
100.48 (C-1), 128.15–128.70 [ϫ 6], 132.79–133.20 [ϫ 4] (C-arom),
137.94 (d, 1JC,P = 14.1 Hz, C-ipsoA), 140.34 (d, 1JC,P = 12.3 Hz, C-
ipsoAЈ) ppm. 31P{1H} NMR (161.9 MHz, CDCl3, 25 °C): δ = –22.8
(s) ppm. C64H101O29P·2H2O (1365.44 + 36.03): calcd. for C 54.85,
H 7.55; found C 55.15, H 7.53. MS (ESI-TOF): m/z (%) = 1387.61
(100) [M + Na]+.
Experimental Section
General Methods: All commercial reagents were used as supplied.
All manipulations were performed in Schlenk-type flasks under N2
with degassed solvent. Solvents were dried by conventional meth-
ods and distilled immediately prior to use. Column chromatog-
raphy was performed on silica gel 60 (particle size 40–63 μm, 230–
240 mesh), dried, in advance, overnight at 150 °C. CDCl3 was
passed down a 5-cm-thick alumina column and stored under N2
over molecular sieves (3 Å). Routine 1H and 13C{1H} NMR spectra
were recorded with Bruker FT instruments (AVANCE 400, 500,
1
600 spectrometers). H NMR spectral data were referenced to re-
sidual protiated solvents (δ = 7.26 ppm for CDCl3, 5.32 ppm for
6A,6B-Dideoxy-6A-diphenylphosphanyl-6B-(2,2Ј-bisphenoxyphos-
CD2Cl2) and 13C chemical shifts are reported relative to deuterated
phanyloxy)-2A,2B,2C,2D,2E, 2F,3A,3B,3C,3D,3E,3F,6C,6D,6E,6F-hexa-
solvents (δ = 77.16 ppm for CDCl3). Mass spectra were recorded deca-O-methyl-α-cyclodextrin (6): Powdered sodium hydride (60%
with a Bruker MicroTOF spectrometer (ESI) by using CH2Cl2,
MeCN or MeOH as solvent. Elemental analyses were performed
by the Service de Microanalyse, Institut de Chimie UMR 7177,
Strasbourg. Melting points were determined with a Büchi 535 cap-
illary melting point apparatus. Optical rotations were measured on
a Perkin–Elmer 341 digital polarimeter with a path length of 1 dm.
The catalytic solutions were analysed by using a Varian 3900 gas
chromatograph equipped with a wall-coated open tubular fused-
silica column (25 mϫ 0.25 mm) or with a Chirasil-DEX CB col-
dispersion in oil; 0.019 g, 0.47 mmol) was added to a solution of an-
hydrous 1 (0.255 g, 0.19 mmol) in toluene (7.0 mL). The suspension
was stirred at 100 °C for 16 h before being cooled to 0 °C. A solu-
tion of (1,1Ј-biphenyl-2,2Ј-diyl)chlorophosphite (2; 0.187 g,
0.75 mmol) in toluene (7.5 mL) was then added at 0 °C and the
resulting reaction mixture stirred at 0 °C for 1 h. The temperature
was subsequently raised to 100 °C and the slurry stirred at this
temperature for an additional 16 h. After cooling, the reaction mix-
ture was evaporated to dryness in vacuo. The residue was subjected
umn (25 mϫ 0.25 mm). Phosphane–borane 1·BH3,[7] (1,1Ј-bi- to column chromatography [short pad of Al2O3, CH2Cl2, followed
phenyl-2,2Ј-diyl)chlorophosphite (2),[14] (4,4Ј,6,6Ј-tetra-tert-butyl-
1,1Ј-biphenyl-2,2Ј-diyl)chlorophosphite (3),[14] [(R)-1,1Ј-binaphth-
yl-2,2Ј-diyl]chlorophosphite (4), [(S)-1,1Ј-binaphthyl-2,2Ј-diyl]-
chlorophosphite (5)[15] and [PtCl2(PhCN)2][16] were synthesised ac-
cording to literature procedures. In this publication, the glucose
units are arranged clockwise when looking at the primary face. The
numbering of the atoms within a glucose unit is as follows:
by CH2Cl2/THF (50:50, v/v)]. If necessary, the resulting colourless
solid was further purified by column chromatography (SiO2;
CH2Cl2/THF, 90:10 to 85:15, v/v) to afford analytically pure 6
(0.145 g, 49%). Rf (SiO2, CH2Cl2/MeOH, 90:10, v/v) = 0.72, m.p.
dec. [α]2D0 = +105 (CH2Cl2, c = 4.0). 1H NMR (400.1 MHz, CDCl3,
25 °C): δ = (assignment by combined COSY and HMQC) = 2.55
2
2
3
(dt, J6a-H,6b-H = 14.7, J6b-H,P = J6b-H,5-H = 3.2 Hz, 1 H, 6bA-H),
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M. Jouffroy, D. Sémeril, D. Armspach, D. Matt
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2.60 (ddd, J6a-H,6b-H = 14.7, J6a-H,P = 2.9, J6a-H,5-H = 8.3 Hz, 1 7.41 (d, 4J = 2.3 Hz, 1 H, H-aromB), 7.43–7.47 (2 H, H-
2
2
3
H, 6aA-H), 3.01 (s, 3 H, OMe), 3.07 (dd, J2-H,3-H = 9.9, J2-H,1-H aromA) ppm. 13C{1H} NMR (125.8 MHz, CDCl3, 25 °C): δ =
3
3
3
3
1
= 3.4 Hz, 1 H, 2-H), 3.09 (dd, J2-H,3-H = 10.6, J2-H,1-H = 3.3 Hz, 31.09, 31.12, 31.35, 31.53 [ ϫ 9] (CH3-tBu), 32.54 (d, JC,P
=
1 H, 2-H), 3.14–3.20 (3 H, 2-H), 3.22 (dd, J2-H,3-H = 9.4, J2-H,1-H 13.8 Hz, C-6A), 34.58, 34.53, 35.29, 35.33 (C-tBu), 57.57, 57.59,
3
3
2
3
= 2.9 Hz, 1 H, 2-H), 3.32 (dd, J6-Ha,6b-H = 11.9, J6b-H,5-H
=
57.68, 57.95, 58.20 [ϫ 2], 58.64, 58.80, 59.08 [ϫ 2], 61.55, 61.66,
2
2.2 Hz, 1 H, 6b-H), 3.37 (s, 6 H, OMe), 3.38 (s, 3 H, OMe), 3.44
(s, 3 H, OMe), 3.45 (s, 3 H, OMe), 3.48 (s, 9 H, OMe), 3.51 (s, 3
H, OMe), 3.61 (s, 3 H, OMe), 3.62 (s, 3 H, OMe), 3.63 (s, 6 H,
61.73, 61.87, 61.89, 61.92 (OMe), 62.77 (d, JC,P = 23.3 Hz, C-6B),
70.85 (C-6), 70.99, 71.07, 71.10 (C-5), 71.16 (C-6), 71.18 (C-5),
71.23 (C-6), 71.45, 71.53 (C-5), 71.59 (C-6), 80.82, 81.16, 81.28 [ϫ
OMe), 3.64 (s, 3 H, OMe), 3.67 (s, 3 H, OMe), 3.33–3.96 (25 H, 3- 2], 81.32, 81.42, 81.54, 81.59, 81.73, 81.93, 81.96 [ ϫ 2], 82.08,
2
2
H, 4-H, 5-H, 6-H), 4.14 (ddd, J6a-H,6b-H = 11.8, J6a-H,P = 2.5,
82.41, 82.56, 82.69, 82.74 (C-2, C-3, C-4), 89.15 (d, 3JC,P = 11.6 Hz,
3J6a-H,5-H = 9.4 Hz, 1 H, 6aB-H), 4.22 (ddd, J5-H,6-Hb = 3.2, C-4A), 98.96, 99.48, 99.97, 100.01, 100.58, 100.89 (C-1), 123.77,
3
3J5-H,6a-H = 8.3, J5-H,4-H = 17.7 Hz, 1 H, 5A-H), 4.89 (d, J1-H,2-H 124.08, 126.24, 126.51, 128.18, 128.24, 128.29, 128.58, 128.64,
3
3
= 3.3 Hz, 1 H, 1-H), 4.93 (d, 3J1-H,2-H = 2.9 Hz, 1 H, 1-H), 4.95 (d,
3J1-H,2-H = 3.2 Hz, 1 H, 1-H), 5.05 (d, 3J1-H,2-H = 3.2 Hz, 1 H, 1-H),
5.06 (d, 3J1-H,H,2 = 3.6 Hz, 1 H, 1-H), 5.08 (d, 3J1-H,2-H = 3.4 Hz, 1
H, 1-H), 7.09 (d, J = 7.8 Hz, 1 H, H-arom), 7.12 (d, J = 7.9 Hz, 1
H, H-arom), 7.17–7.50 (16 H, H-arom) ppm. 13C{1H} NMR
(100.6 MHz, CDCl3, 25 °C): δ = (assignment by HMQC) = 31.57
128.85, 132.41, 132.56, 132.97, 133.13, 133.35 (C-arom), 139.22 (d,
1JC,P = 11.6 Hz, C-ipsoA), 139.77, 140.07 (C-arom), 141.24 (d, 1JC,P
= 11.6 Hz, C-ipsoAЈ), 145.44, 145.74, 145.80, 145.85, 146.32 (C-
arom) ppm. 31P{1H} NMR (161.9 MHz, CDCl3, 60 °C): δ = –20.6
(s, PA), 149.2 (br. s, PB) ppm. C92H140O31P2·2H2O (1802.89 +
36.02): calcd. for C 60.05, H 7.89; found C 59.75, H 7.94. MS (ESI-
TOF): m/z (%) = 1826.88 (100) [M + Na]+.
1
(d, JC,P = 14.0 Hz, C-6A), 57.74, 57.78, 57.81, 57.97, 58.11, 58.18,
58.72, 59.05, 59.11 [ϫ 2], 61.69, 61.78 [ϫ 2], 61.87, 61.90 [ϫ 2]
6A,6B-Dideoxy-6A-diphenylphosphanyl-6B-(R)-(1,1Ј-binaphthyl-2,2Ј-
bisoxyphosphanyloxy)-2A,2B,2C,2D,2E,2F,3A,3B,3C,3D,3E,3F,6C,6D,
6E,6F-hexadeca-O-methyl-α-cyclodextrin (8): This compound was
prepared in 49% (0.128 g) according to the procedure used for the
synthesis of 6, by reacting 1 (0.216 g, 0.16 mmol) with [(R)-1,1Ј-
binaphthyl-2,2Ј-diyl]chlorophosphite (4; 0.222 g, 0.63 mmol). Rf
(SiO2, CH2Cl2/MeOH, 90:10, v/v) = 0.72, m.p. dec. [α]2D0 = +20
2
(OMe), 63.37 (d, JC,P = 9.5 Hz, C-6B), 70.89 (C-5A), 71.04 (C-6),
71.09 [ϫ 2] (C-5), 71.19, 71.24 (C-6), 71.33, 71.45 [ϫ 2] (C-5),
71.54 (C-6), 80.89, 81.20, 81.31 [ϫ 2], 81.40, 81.59, 81.68, 81.96,
82.02 [ϫ 2], 82.06 [ϫ 2], 82.15, 82.41, 82.45, 82.55 [ϫ 2] (C-2, C-
3, C-4), 87.66 (C-4A), 99.20, 99.55, 100.04, 100.06, 100.09, 100.47
1
(C-1), 124.96, 125.08 (C-arom), 128.02 (d, JC,P = 10.1 Hz, C-ip-
soA), 128.28, 128.36, 128.42, 128.51, 128.57, 128.70, 128.77, 128.87,
129.01 [ϫ 2], 129.86, 129.92, 130.59, 132.59 (C-arom), 131.50 (d,
1JC,P = 12.5 Hz, C-ipsoЈA), 132.76, 133.04, 133.24, 133.52, 136.14,
138.97 (C-arom) ppm. 31P{1H} NMR (161.9 MHz, CDCl3, 25 °C):
δ = –21.4 (s, PA), 146.6 (s, PB) ppm. C76H108O31P2·CH2Cl2 (1579.60
+ 84.93): calcd. for C 55.56, H 6.66; found C 55.86, H 6.61. MS
(ESI-TOF): m/z (%) = 1601.60 (100) [M + Na]+.
1
(CH2Cl2, c = 5.0); H NMR (400.1 MHz, CDCl3, 25 °C): δ = (as-
2
signment by combined COSY and HSQC) = 2.51 (dt, J6a-H,6b-H
=
2
14.9, J6b-H,P
=
3J6b-H,5-H = 3.4 Hz, 1 H, 6bA-H), 2.61 (ddd,
2J6a-H,6b-H = 14.9, J6a-H,P = 3.1, J6a-H,5-H = 8.4 Hz, 1 H, 6aA-H),
2
3
3
3
3.00 (s, 3 H, OMe), 3.06 (dd, J2-H,3-H = 9.0, J2-H,1-H = 2.9 Hz, 1
H, 2-H), 3.07 (dd, J2-H,3-H = 9.7, J2-H,1-H = 3.3 Hz, 1 H, 2-H),
3
3
3
3
3.15 (dd, J2-H,3-H = 9.9, J2-H,1-H = 3.3 Hz, 1 H, 2-H), 3.18 (s, 3
6A,6B-Dideoxy-6A-diphenylphosphanyl-6B-(4,4Ј,6,6Ј-tetra-tert-butyl-
2,2Ј-bisphenoxyphosphanyloxy)-2A,2B,2C,2D,2E,2F,3A,3B,3C,3D,3E,3F,
6C,6D,6E,6F-hexadeca-O-methyl-α-cyclodextrin (7): This compound
was prepared according to the procedure used for the synthesis of
H, OMe), 3.16–3.22 (2 H, 2-H), 3.24 (dd, 3J2-H,3-H = 9.8, 3J2-H,1-H
=
3.2 Hz, 1 H, 2-H), 3.29 (dd, 2J6b-H,6a-H = 10.9, 3J6b-H,5-H = 1.5 Hz, 1
H, 6b-H), 3.37 (s, 3 H, OMe), 3.42 (m, 1 H, 6bB-H), 3.45 (s, 6 H,
OMe), 3.47 (s, 3 H, OMe), 3.49 (s, 6 H, OMe), 3.50 (s, 3 H, OMe),
6, by reacting 1 (0.200 g, 0.15 mmol) with (4,4Ј,6,6Ј-tetra-tert-butyl- 3.52 (s, 3 H, OMe), 3.57 (s, 3 H, OMe), 3.61 (s, 3 H, OMe), 3.63
1,1Ј-biphenyl-2,2Ј-diyl)chlorophosphite (3; 0.278 g, 0.58 mmol).
The crude mixture was subjected to column chromatography (SiO2;
CH2Cl2/MeOH, 97:3, v/v) to afford 7 (0.164 g, 62%) as a colourless
(s, 3 H, OMe), 3.64 (s, 3 H, OMe), 3.65 (s, 3 H, OMe), 3.67 (s, 3
H, OMe), 3.44–3.99 (24 H, 3-H, 4-H, 5-H, 6-H), 4.17 (t,
2J6a-H,6b-H
=
3J6a-H,5-H = 10.5 Hz, 1 H, 6aB-H), 4.22 (ddd,
3
3
solid. Rf (SiO2, CH2Cl2/MeOH, 90:10, v/v) = 0.72, m.p. dec. [α]2D0
3J5-H,6b-H = 3.4, J5-H,6a-H = 8.4, J5-H,4-H = 17.7 Hz, 1 H, 5A-H),
1
3
3
= +140 (CH2Cl2, c = 5.0); H NMR (500.1 MHz, CDCl3, 25 °C): 4.77 (d, J1-H,2-H = 3.3 Hz, 1 H, 1-H), 4.93 (d, J1-H,2-H = 3.2 Hz,
3
3
δ = (assignment by COSY) = 1.34 (s, 9 H, tBu), 1.35 (s, 9 H, tBu),
1 H, 1-H), 4.99 (d, J1-H,2-H = 2.9 Hz, 1 H, 1-H), 5.05 (d, J1-H,2-H
= 3.1 Hz, 1 H, 1-H), 5.07 (d, 3J1-H,2-H = 3.1 Hz, 1 H, 1-H), 5.11 (d,
3J1-H,2-H = 3.3 Hz, 1 H, 1-H), 7.14–7.49 (17 H, H-arom), 7.77–7.99
2
144 (s, 9 H, tBu), 1.46 (s, 9 H, tBu), 2.37 (ddd, J6a-H,6b-H = 14.9,
3
2J6a-H,P = 2.9, J6a-H,5-H = 10.7 Hz, 1 H, 6aA-H), 2.67 (dt,
2
2J6a-H,6b-H = 14.9, J6b-H,P = 3J6b-H,5-H = 2.8 Hz, 1 H, 6bA-H), 3.05 (5 H, H-arom) ppm. 13C{1H} NMR (100.6 MHz, CDCl3, 25 °C): δ
3
3
(s, 3 H, OMe), 3.08 (dd, J2-H,3-H = 10.1, J2-H,1-H = 2.9 Hz, 1 H,
= (assignment by HSQC) = 32.15 (d, 1JC,P = 14.3 Hz, C-6A), 57.48,
3
3
2-H), 3.09 (dd, J2-H,3-H = 10.1, J2-H,1-H = 3.1 Hz, 1 H, 2-H), 3.15 57.78, 57.82, 57.95, 58.13, 58.26, 58.67, 59.12 [ϫ 2], 59.18, 61.69,
(dd, J2-H,3-H = 10.1, J2-H,1-H = 3.2 Hz, 1 H, 2-H), 3.20 (dd, J2-
3
3
3
2
61.70, 61.73, 61.86, 61.89, 61.92 (OMe), 63.34 (d, JC,P = 16.6 Hz,
3
3
= 9.7, J2-H,1-H = 3.3 Hz, 1 H, 2-H), 3.21 (dd, J2-H,3-H = 9.2,
C-6B), 71.06 [ϫ 2], 71.11 (C-5), 71.17, 71.22 (C-6), 71.32 (C-5),
71.40 (C-6), 71.45 [ϫ 2] (C-5), 71.53 (C-6), 80.79, 81.18, 81.33 [ϫ
4], 81.40, 81.60, 81.74, 81.99 [ ϫ 2], 82.17, 82.23, 82.43, 82.45,
H,3-H
3J2-H,1-H = 3.7 Hz, 1 H, 2-H), 3.22 (dd, 3J2-H,3-H = 10.1, 3J2-H,1-H
=
3.2 Hz, 1 H, 2-H), 3.36 (s, 3 H, OMe), 3.37 (s, 3 H, OMe), 3.46 (s,
3 H, OMe), 3.47 (s, 3 H, OMe), 3.48 (s, 3 H, OMe), 3.49 (s, 3 H,
OMe), 3.50 (s, 3 H, OMe), 3.51 (s, 3 H, OMe), 3.52 (s, 3 H, OMe),
3.58 (s, 3 H, OMe), 3.62 (s, 3 H, OMe), 3.63 (s, 3 H, OMe), 3.64
(s, 6 H, OMe), 3.65 (s, 3 H, OMe), 3.33–3.96 (27 H, 3-H, 4-H, 5-
H, 6-H), 4.24 (m, 1 H, 5A-H), 4.85 (d, 3JH-1,2-H = 3.7 Hz, 1 H, 1-H),
4.95 (d, 3J1-H,2-H = 3.1 Hz, 1 H, 1-H), 5.02 (d, 3J1-H,2-H = 3.2 Hz, 1
3
82.61, 82.62 (C-2, C-3, C-4), 88.00 (d, JC,P = 11.2 Hz, C-4A),
99.09, 99.20, 100.03, 100.11, 100.35, 100.48 (C-1), 121.86, 122.52,
124.03, 124.28, 124.80, 125.06, 125.33, 126.04, 126.26, 127.00,
127.11, 127.47, 128.16, 128.34, 128.39, 128.43, 128.60, 128.67,
128.86, 129.06, 129.44, 130.23, 131.02, 131.40, 131.50, 132.36,
132.54, 133.07, 133.28, 139.69, 140.65, 141.44 (C-arom) ppm.
31P{1H} NMR (161.9 MHz, CDCl3, 25 °C): δ = –20.3 (s, PA), 148.9
(s, PB) ppm. C84H112O31P2·H2O (1679.72 + 18.01): calcd. for C
59.43, H 6.77; found C 59.72, H 6.99. MS (ESI-TOF): m/z (%) =
1701.66 (100) [M + Na]+.
3
3
H, 1-H), 5.07 (d, J1-H,2-H = 3.2 Hz, 1 H, 1-H), 5.08 (d, J1-H,2-H
=
3
3.3 Hz, 1 H, 1-H), 5.12 (d, J1-H,2-H = 2.9 Hz, 1 H, 1-H), 7.14 (d,
4J = 2.4 Hz, 1 H, H-aromB), 7.15 (d, J = 2.3 Hz, 1 H, H-aromB),
4
7.19–7.33 (8 H, H-aromA), 7.40 (d, 4J = 2.4 Hz, 1 H, H-aromB),
6074
www.eurjoc.org
© 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 2013, 6069–6077

Phosphane-Phosphite Chelators Built on a α-Cyclodextrin Scaffold
6A,6B-Dideoxy-6A-diphenylphosphanyl-6B-(S)-(1,1Ј-binaphthyl-2,2Ј- (dd, JC,PA = 10.5, JC,PB = 8.0 Hz, C-6A), 57.66 [ϫ 2], 57.82 [ϫ
1
3
bisoxyphosphanyloxy)-2A,2B,2C,2D,2E,2F,3A,3B,3C,3D,3E,3F,6C,6D,
6E,6F-hexadeca-O-methyl-α-cyclodextrin (9): This compound was
prepared in 37% (0.110 g) according to the procedure used for the
synthesis of 6, by reacting 1 (0.245 g, 0.18 mmol) with [(S)-1,1Ј-
binaphthyl-2,2Ј-diyl]chlorophosphite (5; 0.252 g, 0.72 mmol). Rf
(SiO2, CH2Cl2/MeOH, 90:10, v/v) = 0.72, m.p. dec. [α]2D0 = +224
2], 58.02, 58.29 [ϫ 2], 58.85, 59.09, 59.22, 59.67, 61.30, 61.56 [ϫ
2
4
2], 61.86 [ϫ 2] (OMe), 70.01 (virtual t, JC,PB = JC,PA = 16.0 Hz,
C-6B), 70.54, 71.12 (C-6), 71.24, 71.52 [ ϫ 2, C-5), 71.59 (C-6),
71.72 [ϫ 3] (C-5), 72.01 (C-6), 80.42 [ϫ 2], 80.67 [ϫ 2], 81.16 [ϫ
2], 81.28, 81.37, 81.82, 81.87, 82.08 [ϫ 3], 82.15, 82.30, 82.44, 82.56
(C-2, C-3, C-4), 83.76 (d, 3JC,P = 9.8 Hz, C-4A), 98.30, 99.45, 99.77,
100.31, 100.38, 100.62 (C-1), 126.26, 126.43 [ϫ 2], 127.63, 127.76,
127.86, 127.94, 128.03, 128.55, 128.85, 129.21, 129.52, 129.65,
129.74 [ϫ 2], 130.26 [ϫ 2], 130.86, 130.92, 132.34, 134.06 [ϫ 2]
1
(CH2Cl2, c = 5.0); H NMR (400.1 MHz, CDCl3, 25 °C): δ = (as-
2
signment by combined COSY and HSQC) = 2.64 (dt, J6a-H,6b-H
=
2
14.6, J6b-H,P
=
3J6b-H,5-H = 3.2 Hz, 1 H, 6bA-H), 2.71 (ddd,
2J6a-H,6b-H = 14.8, J6a-H,P = 2.6, J6a-H,5-H = 7.4 Hz, 1 H, 6aA-H), (C-arom), 148.13 (dd, JC,PA = 9.1, JC,PB = 3.0 Hz, C-ipsoA),
2
3
1
3
3
3
1
3
3.02 (dd, J2-H,3-H = 9.0, J2-H,1-H = 3.1 Hz, 1 H, 2-H), 3.04 (s, 3
H, OMe), 3.12–3.19 (4 H, 2-H), 3.22 (dd, J2-H,3-H = 10.1, J2-H,1- NMR (161.9 MHz, CDCl3, 60 °C): δ = 6.7 (d with Pt satellites,
148.50 (dd, JC,PA = 10.1, JC,PB = 3.1 Hz, C-ipsoAЈ) ppm. 31P{1H}
3
3
1
= 3.1 Hz, 1 H, 2-H), 3.34 (s, 3 H, OMe), 3.35 (s, 3 H, OMe),
2JPA,PB = 22.7, JPA,Pt = 3407.9 Hz, PA), 82.1 (d with Pt satellites,
H
1
3.37 (s, 3 H, OMe), 3.43 (s, 3 H, OMe), 3.48 (s, 9 H, OMe), 3.49
(s, 3 H, OMe), 3.52 (s, 3 H, OMe), 3.61 (s, 3 H, OMe), 3.63 (s, 9
H, OMe), 3.64 (s, 3 H, OMe), 3.67 (s, 3 H, OMe), 3.31–3.93 (26
2JPB,PA = 22.7, JPB,Pt = 6136.4 Hz, PB) ppm. C76H108Cl2O31P2Pt
(1845.45): calcd. for C 49.46, H 5.90; found C 49.23, H 6.08. MS
(ESI-TOF): m/z (%) = 1826.60 (100) [M – Cl + H2O]+, 1867.63
(48) [M + Na]+.
2
3
H, 3-H, 4-H, 5-H, 6-H), 4.14 (t, J6a-H,6b-H = J6a-H,5-H = 10.8 Hz,
1 H, 6aB-H), 4.23 (ddd, J5-H,6b-H = 3.2, J5-H,6a-H = 7.4, J5-H,4-H
3
3
3
cis-P,PЈ-(Cycloocta-1,5-diene)-[6A,6B-dideoxy-6A-diphenylphos-
phanyl-6B-(2,2Ј-bisphenoxyphosphanyloxy)-2A,2B,2C,2D,2E,2F,3A,3B,3C,
3D,3E,3F,6C,6D,6E,6F-hexadeca-O-methyl-α-cyclodextrin]rhodium (I)
(11): A solution of [Rh(COD)2]BF4 (0.031 g, 0.08 mmol) in CH2Cl2
(2 mL) was added dropwise to a solution of 6 (0.120 g, 0.08 mmol)
in CH2Cl2 (4 mL) under vigorous stirring. After 5 min, the volume
of the reaction mixture was reduced to 1 mL and pentane (20 mL)
was added to precipitate 11, which was collected by filtration to
afford a bright yellow powder (0.141 g, 99%). Rf (SiO2, CH2Cl2/
MeOH, 90:10, v/v) = 0.30, m.p. dec. 1H NMR (400.1 MHz, CDCl3,
25 °C): δ = (assignment by COSY) = 1.55–1.66 (br. m, 1 H, allylic
protons of COD), 1.73–1.82 (br. m, 1 H, allylic protons of COD),
1.98–2.33 (6 H, allylic protons of COD), 2.35 (s, 3 H, OMe), 2.97
(s, 3 H, OMe), 3.25 (s, 3 H, OMe), 3.35 (s, 3 H, OMe), 3.41 (s, 3
H, OMe), 3.47 (s, 3 H, OMe), 3.48 (s, 3 H, OMe), 3.49 (s, 3 H,
OMe), 3.51 (s, 3 H, OMe), 3.53 (s, 3 H, OMe), 3.55 (s, 3 H, OMe),
3.57 (s, 3 H, OMe), 3.58 (s, 3 H, OMe), 3.59 (s, 3 H, OMe), 3.62
(s, 6 H, OMe), 2.65–4.31 (37 H, 1-H, 2-H, 3-H, 4-H, 5-H, 6-H),
4.33 (m, 1 H, vinylic protons of COD), 4.40 (m, 1 H, 1-H), 4.93
(m, 1 H, vinylic protons of COD), 5.00 (d, 3J1-H,2-H = 3.1 Hz, 1 H,
3
= 17.0 Hz, 1 H, 5A-H), 4.82 (d, J1-H,2-H = 3.3 Hz, 1 H, 1-H), 4.94
3
(d, J1-H,2-H = 3.1 Hz, 2 H, 1-H), 5.04–5.07 (3 H, 1-H), 7.18–7.54
(18 H, H-arom), 7.82 (d, J = 8.7 Hz, 1 H, H-arom), 7.85 (d, J =
8.2 Hz, 1 H, H-arom), 7.90–7.97 (2 H, H-arom) ppm. 13C{1H}
NMR (125.8 MHz, CDCl3, 25 °C): δ = (assignment by HSQC) =
1
32.15 (d, JC,P = 14.2 Hz, C-6A), 57.65, 57.77, 57.85, 58.00, 58.08,
58.14, 58.76, 59.11 [ϫ 3], 61.66, 61.80 [ϫ 2], 61.83, 61.89 [ϫ 2]
2
(OMe), 63.46 (d, JC,P = 15.2 Hz, C-6B), 71.10 [ϫ 2] (C-5), 71.18,
71.24 (C-6), 71.33, 71.39, 71.41, 71.46 (C-5), 71.56 [ϫ 2] (C-6),
80.91, 81.21, 81.24, 81.27, 81.38, 81.45, 81.75, 81.93, 82.06, 82.15
[ϫ 2], 82.20, 82.29, 82.33, 82.47, 82.50, 82.56 (C-2, C-3, C-4), 87.89
3
(d, JC,P = 10.5 Hz, C-4A), 99.35, 99.58, 100.0, 100.02, 100.04,
2
100.43 (C-1), 120.57 (d, JC,P = 6.5 Hz, C-ipsoB), 121.84, 122.12,
2
122.92 (C-arom), 124.36 (d, JC,P = 5.2 Hz, C-ipsoBЈ), 124.86,
125.02, 126.13, 126.22, 127.03, 127.05, 128.15, 128.27, 128.34,
128.41 [ϫ 2], 128.47, 128.50, 128.56, 128.73, 129.36, 130.22, 131.02,
131.49, 132.74, 132.89 [ϫ 2], 132.96, 133.11 (C-arom), 139.41 (d,
1
1JC,P = 11.8 Hz, C-ipsoA), 140.82 (d, JC,P = 12.0 Hz, C-ipsoAЈ),
147.47 (C-arom) ppm. 31P{1H} NMR (161.9 MHz, CDCl3, 25 °C):
δ = –20.9 (s, PA), 150.7 (s, PB) ppm. C84H112O31P2·CHCl3 (1679.72
+ 119.38): calcd. for C 56.75, H 6.33; found C 56.75, H 6.65. MS
(ESI-TOF): m/z (%) = 1701.66 (100) [M + Na]+.
3
3
1-H), 5.08 (d, J1-H,2-H = 2.9 Hz, 1 H, 1-H), 5.09 (d, J1-H,2-H
=
3
3.2 Hz, 1 H, 1-H), 5.10 (d, J1-H,2-H = 3.0 Hz, 1 H, 1-H), 5.35 (m,
1 H, vinylic protons of COD), 5.92 (m, 1 H, vinylic protons of
COD), 7.01–7.59 (12 H, H-arom), 7.64–7.97 (4 H, H-arom), 8.30
(m, 2 H, H-arom) ppm. 31P{1H} NMR (161.9 MHz, CDCl3,
25 °C): δ = 21.7 (dd, 1JPA,Rh = 142.0, 2JPA,PB = 40.9 Hz, PA), 121.2
cis-P,PЈ-Dichloro-[6A,6B-dideoxy-6A-diphenylphosphanyl-6B-(2,2Ј-bis-
phenoxyphosphanyloxy)-2A,2B,2C,2D,2E,2F,3A,3B,3C,3D,3E,3F,6C,6D,
6E,6F-hexadeca-O-methyl-α-cyclodextrin]platinum (II) (10): A solu-
tion of [PtCl2(PhCN)2] (0.009 g, 0.02 mmol) in CH2Cl2 (1 mL) was
added dropwise to a solution of 6 (0.030 g, 0.02 mmol) in CH2Cl2
(2 mL) under vigorous stirring. After 5 min, the reaction mixture
was evaporated to dryness in vacuo to afford analytically pure 10
(0.035 g, 99%) as a pale yellow solid. Rf (SiO2, CH2Cl2/MeOH,
90:10, v/v) = 0.74, m.p. dec. 1H NMR (400.1 MHz, CDCl3, 25 °C):
δ = (assignment by combined COSY and HSQC) = 1.70 (m, 1 H,
6B-H), 3.01 (s, 3 H, OMe), 3.09 (s, 3 H, OMe), 3.10–3.21 (6 H, 2-
( d d , J P B , R h = 2 6 9 . 2 , J P B , P A = 4 0 . 9 H z , P B ) p p m .
C84H120BF4O31P2Rh·CH2Cl2 (1877.49 + 84.93): calcd. for C 52.02,
H 6.27; found C 52.00, H 6.50. MS (ESI-TOF): m/z (%) = 1681.54
(100) [M – COD – BF4]+.
1
2
cis-P,PЈ-(Cycloocta-1,5-diene)-[6A,6B-dideoxy-6A-diphenylphosphan-
yl-6B-(4,4Ј,6,6Ј-tetra-tert-butyl-2,2Ј-bisphenoxyphosphanyloxy)-
2A,2B,2C,2D,2E,2F,3A,3B,3C,3D,3E,3F,6C,6D,6E,6F-hexadeca-O-methyl-
α-cyclodextrin]rhodium (I) (12): This compound was prepared in
99% yield (0.155 g) according to the procedure used for 11, by
reacting 7 (0.134 g, 0.07 mmol) with [Rh(COD)2]BF4 (0.030 g,
0.07 mmol). Rf (SiO2, CH2Cl2/MeOH, 90:10, v/v) = 0.30, m.p. dec.
3
3
H, 6A-H), 3.27 (dd, J2-H,3-H = 9.2, J2-H,1-H = 3.1 Hz, 1 H, 2-H),
3.36 (s, 3 H, OMe), 3.43 (s, 3 H, OMe), 3.47 (s, 3 H, OMe), 3.48
(s, 3 H, OMe), 3.50 (s, 6 H, OMe), 3.51 (s, 3 H OMe), 3.52 (s, 6
H, OMe), 3.61 (s, 3 H, OMe), 3.63 (s, 9 H, OMe), 3.64 (s, 3 H 1H NMR (400.1 MHz, CDCl3, 60 °C): δ = (assignment by COSY)
OMe), 3.45–3.71 (15 H, 3-H, 4-H, 6-H), 3.71–3.85 (5 H, 6-H), 3.86–
= 1.33 (s, 9 H, tBu), 1.40 (s, 9 H, tBu), 1.59 (s, 9 H, tBu), 1.88 (s,
4.08 (5 H, 4-H, 5-H), 4.30 (m, 1 H, 5A-H), 4.45 (br. m, 1 H, 5B- 9 H, tBu), 1.98–2.08 (br. m, 1 H, allylic protons of COD), 2.18–
3
H), 4.78 (d, J1-H,2-H = 3.2 Hz, 1 H, 1-H), 4.84 (br. m, 1 H, 6-HA),
2.31 (br. m, 1 H, allylic protons of COD), 2.32–2.56 (6 H, allylic
3
4.86 (m, 1 H, 1-H), 5.05 (m, 2 H, 1-H), 5.12 (d, J1-H,2-H = 3.4 Hz,
protons of COD), 2.41 (t, 3J4-H,3-H = 3J4-H,5-H = 8.4 Hz, 1 H, 4-H),
1 H, 1-H), 5.25 (br. m, 1 H, 1-H), 7.20–7.46 (10 H, H-arom), 7.56– 2.80–2.87 (2 H, 2-H, 6-H), 2.97–3.03 (2 H, 2-H), 3.10 (s, 3 H,
7.62 (4 H, H-arom), 7.84–7.93 (4 H, H-arom) ppm. 13C{1H} NMR OMe), 3.29 (s, 3 H, OMe), 3.32 (s, 3 H, OMe), 3.40 (s, 3 H, OMe),
(125.8 MHz, CDCl3, 50 °C): δ = (assignment by HSQC) = 24.90
3.46 (s, 3 H, OMe), 3.47 (s, 3 H, OMe), 3.49 (s, 3 H, OMe), 3.52
6075
Eur. J. Org. Chem. 2013, 6069–6077
© 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org

M. Jouffroy, D. Sémeril, D. Armspach, D. Matt
FULL PAPER
(s, 3 H, OMe), 3.53 (s, 3 H, OMe), 3.54 (s, 3 H, OMe), 3.56 (s, 6
H, OMe), 3.57 (s, 3 H, OMe), 3.58 (s, 3 H, OMe), 3.61 (s, 6 H,
OMe), 3.05–3.97 (29 H, 2-H, 3-H, 4-H, 5-H, 6-H), 3.99–4.08 (3 H,
1-H, 5-H, vinylic protons of COD), 4.13 (m, 1 H, vinylic protons
of COD), 4.28 (m, 1 H, 5-H), 4.35 (m, 1 H, 1-H), 4.76 (d,
3J1-H,2-H = 2.8 Hz, 1 H, 1-H), 4.83 (m, 1 H, vinylic protons of
COD), 5.05–5.10 (3 H, 1-H), 5.83 (m, 1 H, vinylic protons of
COD), 7.12–7.19 (3 H, H-arom), 7.35–7.45 (4 H, H-arom), 7.52 (s,
1 H, H-arom), 7.53–7.59 (2 H, H-arom), 7.62 (s, 1 H, H-arom), 7.83
(m, 1 H, H-arom), 8.30–8.38 (2 H, H-arom) ppm. 31P{1H} NMR
55.87, H 6.32; found C 55.68, H 6.57. MS (ESI-TOF): m/z (%) =
1781.55 (100) [M – COD – BF4]+.
cis-P,PЈ-(Cycloocta-1,5-diene)-[6A,6B-dideoxy-6A-diphenylphosphan-
yl-6B-(S)-(1,1Ј-binaphthyl-2,2Ј-bisoxyphosphanyloxy)-2A,2B,2C,2D,
2E,2F,3A,3B,3C,3D,3E,3F,6C,6D,6E,6F-hexadeca-O-methyl-α-cyclodex-
trin]rhodium (I) (14): This compound was prepared in 99% yield
(0.110 g) according to the procedure used for the synthesis of 11,
by reacting 9 (0.095 g, 0.06 mmol) with [Rh(COD)2]BF4 (0.023 g,
0.06 mmol). Rf (SiO2, CH2Cl2/MeOH, 90:10, v/v) = 0.30, m.p. dec.
1H NMR (400.1 MHz, CDCl3, 25 °C): δ = (assignment by com-
bined COSY and HSQC) = 1.71 (br. m, 1 H, allylic protons of
COD), 1.91 (br. m, 1 H, allylic protons of COD), 2.00–2.29 (6 H,
1
2
(161.9 MHz, CDCl3, 60 °C): δ = 19.6 (dd, JPA,Rh = 142.9, JPA,PB
1
2
= 37.4 Hz, PA), 121.1 (dd, JPB,Rh = 266.7, JPB,PA = 37.4 Hz,
PB) ppm. C100H152BF4O31P2Rh·2CH2Cl2 (2101.92 + 169.87): calcd.
for C 53.93, H 6.92; found C 54.02, H 7.18. MS (ESI-TOF): m/z
(%) = 1905.80 (100) [M – COD – BF4]+, 2014.90 (6) [M – BF4]+.
3
3
allylic protons of COD), 2.38 (dd, J2-H,3-H = 9.6, J2-H,1-H
=
3.1 Hz, 1 H, 2-HA), 2.81 (br. d, J6a-H,6b-H = 9.6 Hz, 1 H, 6-H),
2
3
2.84 (t, J4-H,3-H
=
3J4-H,5-H = 8.7 Hz, 1 H, 4B-H), 2.88 (s, 3 H,
OMe), 2.91 (dd, 2J6a-H,6b-H = 11.7, 3J6b-H,5-H = 2.3 Hz, 1 H, 6b-H),
cis-P,PЈ-(Cycloocta-1,5-diene)-[6A,6B-dideoxy-6A-diphenylphosphan-
yl-6B-(R)-(1,1Ј-binaphthyl-2,2Ј-bisoxyphosphanyloxy)-2A,2B,2C,2D,
2E,2F,3A,3B,3C,3D,3E,3F,6C,6D,6E,6F-hexadeca-O-methyl-α-cyclodex-
trin]rhodium (I) (13): This compound was prepared in 99% yield
(0.126 g) according to the procedure used for the synthesis of 11,
by reacting 8 (0.108 g, 0.06 mmol) with [Rh(COD)2]BF4 (0.026 g,
0.06 mmol). Rf (SiO2, CH2Cl2/MeOH, 90:10, v/v) = 0.30, m.p. dec.
1H NMR (400.1 MHz, CDCl3, 60 °C): δ = (assignment by COSY
and HSQC) = 1.68–1.84 (br. m, 1 H, allylic protons of COD), 1.94–
2.05 (br. m, 1 H, allylic protons of COD), 2.07–2.17 (4 H, allylic
2
3
3.00 (dd, J6a-H,6b-H = 11.7, J6b-H,5-H = 2.9 Hz, 1 H, 6b-H), 3.02
3
(s, 3 H, OMe), 3.04–3.10 (3 H, 2-H), 3.11 (dd, J2-H,3-H = 10.2,
3J2-H,1-H = 3.9 Hz, 1 H, 2B-H), 3.15–3.22 (3 H, 2-H, 3-H, 6-H),
2
3
3.23 (dd, J6a-H,6b-H = 9.7, J6b-H,5-H = 2.0 Hz, 1 H, 6b-H), 3.28 (s,
3 H, OMe), 3.33 (s, 3 H, OMe), 3.40 (s, 3 H, OMe), 3.44 (s, 3 H,
OMe), 3.45 (s, 3 H, OMe), 3.46 (s, 3 H, OMe), 3.47 (s, 3 H, OMe),
3.48 (s, 3 H, OMe), 3.51 (s, 3 H, OMe), 3.55 (s, 3 H, OMe), 3.58
(s, 3 H, OMe), 3.59 (s, 3 H, OMe), 3.61 (s, 3 H, OMe), 3.62 (s, 3
H, OMe), 3.27–3.68 (17 H, 1-H, 3-H, 4-H, 5-H, 6-H), 3.72–3.77 (2
2
H, 5-H, vinylic protons of COD), 3.79 (d, J6a-H,6b-H = 10.2 Hz, 1
3
3
protons of COD), 2.40 (t, J4-H,3-H = J4-H,5-H = 9.6 Hz, 1 H, 4B-
H, 6-H), 3.86 (m, 1 H, 5-H), 3.88–3.95 (2 H, 6-H, 6B-H), 4.30 (m,
3
H), 2.34–2.46 (2 H, allylic protons of COD), 2.84 (dd, J2-H,3-H
=
1 H, 6A-H), 4.40 (m, 1 H, 5A-H), 4.50 (d, J1-H,2-H = 2.5 Hz, 1 H,
3
3
2
9.9, J2-H,1-H = 3.5 Hz, 1 H, 2-H), 2.90 (dd, J6a-H,6b-H = 11.7,
1-H), 4.56 (m, 1 H, vinylic protons of COD), 4.67 (m, 1 H, vinylic
3J6b-H,5-H = 2.5 Hz, 1 H, 6bA-H), 3.01 (s, 3 H, OMe), 3.01–3.03 (m,
3
protons of COD), 4.90 (d, J1-H,2-H = 3.2 Hz, 1 H, 1-H), 4.92 (d,
1 H, 6aA-H), 3.05 (dd, J2-H,3-H = 9.7, J2-H,1-H = 3.3 Hz, 1 H, 2-
H), 3.26 (s, 3 H, OMe), 3.29 (s, 3 H, OMe), 3.38 (s, 3 H, OMe),
3.47 (s, 3 H, OMe), 3.48 (s, 3 H, OMe), 3.50 (s, 3 H, OMe), 3.51
(s, 3 H, OMe), 3.52 (s, 3 H, OMe), 3.56 (s, 3 H, OMe), 3.57 (s, 3
H, OMe), 3.59 (s, 3 H, OMe), 3.60 (s, 3 H, OMe), 3.63 (s, 3 H,
OMe), 3.64 (s, 3 H, OMe), 3.65 (s, 3 H, OMe), 3.14–3.87 (25 H, 2-
H, 3-H, 4-H, 5-H, 6-H), 3.91–3.96 (m, 1 H, 5-H), 3.99–4.10 (4 H,
3
3
3
3J1-H,2-H = 3.3 Hz, 1 H, 1-H), 5.02 (d, J1-H,2-H = 3.2 Hz, 1 H, 1-
3
H), 5.04 (d, J1-H,2-H = 3.1 Hz, 1 H, 1-H), 5.40 (m, 1 H, vinylic
protons of COD), 7.23–7.54 (10 H, H-arom), 7.62–7.67 (3 H, H-
arom), 7.72–7.78 (2 H, H-arom), 7.83 (d, J = 9.5 Hz, 1 H, H-arom),
7.89 (d, J = 9.8 Hz, 1 H, H-arom), 7.99 (d, J = 9.6 Hz, 1 H, H-
arom), 8.02 (d, J = 10.1 Hz, 1 H, H-arom), 8.05–8.10 (2 H, H-
arom), 8.31 (d, J = 10.2 Hz, 1 H, H-arom) ppm. 13C{1H} NMR
(125.8 MHz, CDCl3, 25 °C): δ = (assignment by HSQC) = 28.85
3
5-H, 6-H), 4.15 (d, J1-H,2-H = 3.3 Hz, 1 H, 1-H), 4.19 (m, 1 H,
vinylic protons of COD), 4.33 (m, 1 H, 5-H), 4.41 (d, J1-H,2-H
3
=
1
(d, JC,P = 18.9 Hz, C-6A), 29.64–29.94 (4 C, allylic C of COD),
2.6 Hz, 1 H, 1-H), 4.45 (m, 1 H, vinylic protons of COD), 5.04 (d,
3J1-H,2-H = 3.2 Hz, 1 H, 1-H), 5.07 (d, 3J1-H,2-H = 3.1 Hz, 1 H, 1-H),
5.08 (d, 3J1-H,2-H = 3.1 Hz, 1 H, 1-H), 5.10 (d, 3J1-H,2-H = 3.5 Hz, 1
H, 1-H), 5.25 (m, 1 H, vinylic protons of COD), 5.58 (m, 1 H,
vinylic protons of COD), 7.14–7.60 (14 H, H-arom), 7.80 (t, J =
7.3 Hz, 1 H, H-arom), 7.88–8.07 (4 H, H-arom), 8.33–8.41 (3 H,
H-arom) ppm. 13C{1H} NMR (125.8 MHz, CDCl3, 25 °C): δ = (as-
signment by HSQC) = 28.58–28.80 (4 C, allylic C of COD), 31.0
57.53, 58.10, 58.15 [ϫ 2], 58.23, 58.29, 58.84, 59.11, 59.16, 59.88,
3
61.04, 61.18, 61.36, 61.44, 61.69, 61.92 (OMe), 68.47 (d, JC,P
=
2
4.9 Hz, C-5B), 69.14 (d, JC,P = 14.0 Hz, C-6B), 70.00, 70.59 (C-6),
71.26 (d, 2JC,P = 23.3 Hz, C-5A), 71.34, 71.38 (C-5), 71.43 [ϫ 2, C-
6), 71.76, 72.32 (C-5), 79.96, 80.21, 80.83, 80.91, 81.03, 81.10,
81.27, 81.52, 81.70, 81.88, 82.02, 82.28, 82.42, 82.47 [ϫ 2], 82.72,
83.64 (C-2, C-3, C-4), 88.19 (d, 3JC,P = 7.1 Hz, C-4A), 94.40 (vinylic
C of COD), 98.53, 98.71, 99.44, 99.85, 100.37 [ϫ 2] (C-1), 100.16,
108.48, 112.75 (vinylic C of COD), 120.27, 121.47, 122.52, 122.43,
126.08, 126.21, 126.79, 127.04, 127.07, 127.80, 128.19, 128.27,
128.28, 128.41, 128.89, 128.96, 129.04, 129.62, 129.97, 130.84,
130.98, 131.20, 131.92, 132.17, 132.45, 132.80, 133.51, 133.60,
133.65, 133.74, 146.64 (d, 1JC,P = 6.6 Hz, C-ipsoA), 148.75 (d, 1JC,P
= 13.8 Hz, C-ipsoAЈ) ppm. 31P{1H} NMR (161.9 MHz, CDCl3,
25 °C): δ = 20.7 (dd, 1JPA,Rh = 139.7, 2JPA,PB = 41.3 Hz, PA), 122.6
1
(d, JC,P = 20.6 Hz, C-6A), 56.44, 56.56, 56.59, 56.69, 56.83, 56.90,
57.18, 57.33, 57.96, 58.06, 58.12, 60.60, 60.78, 60.80, 60.90, 60.92,
3
(OMe), 65.62 (d, JC,P = 6.3 Hz, C-5B), 66.81 (C-6), 69.05, 69.16
2
(C-5), 69.54 (d, JC,P = 14.1 Hz, C-6B), 69.65 (C-5), 69.97, 70.15
2
(C-6), 70.29 (d, JC,P = 19.2 Hz, C-5A), 71.24 (C-5),71.41 (C-6),
77.69, 77.82, 80.84, 81.21, 81.32, 81.38, 81.47, 81.58, 81.79 [ϫ 2],
82.40, 82.54, 82.60, 82.63, 82.91, 82.96, 83.07 (C-2, C-3, C-4), 87.03
3
(d, JC,P = 13.5 Hz, C-4A), 94.84 (vinylic C of COD), 97.21, 97.48,
(dd, 1JPB,Rh
=
2708, 2JPB,PA
=
41.3 Hz, PB) ppm.
99.09, 99.39, 99.71, 100.27 (C-1), 100.45, 106.02, 111.49, (vinylic C
of COD), 116.74, 119.37, 119.74, 123.05, 123.29, 124.29, 124.73,
124.83, 125.72, 125.80, 126.11, 126.29, 126.44, 127.22, 127.40,
127.44, 128.03, 128.38, 128.49, 128.82, 128.93, 129.02, 129.70,
129.79, 129.95, 130.37, 130.63, 130.78, 132.42, 132.67, 145.21 (d,
C92H124BF4O31P2Rh·2CH2Cl2 (1977.62 + 169.87): calcd. for C
52.57, H 6.01; found C 52.59, H 6.30. MS (ESI-TOF): m/z (%) =
1781.62 (100) [M – COD – BF4]+.
General Procedure for Hydrogenation Experiments: Hydrogenation
1JC,P = 9.1 Hz, C-ipsoA), 146.36 (d, 1JC,P = 11.9 Hz, C-ipsoAЈ) ppm. experiments were carried out in a glass-lined, 100 mL stainless steel
1
31P{1H} NMR (161.9 MHz, CDCl3, 60 °C): δ = 21.9 (dd, JPA,Rh
autoclave containing a magnetic stirring bar. In a typical run, the
2
= 142.0, JPA,PB = 42.0 Hz, PA), 122.1 (dd, 1JPB,Rh = 270.0, 2JPB,PA autoclave was charged with preformed rhodium complexes 11–14
= 42.0 Hz, PB) ppm. C92H124BF4O31P2Rh (1977.62): calcd. for C
(0.01 mmol) and substrate 15–19 (1.0 mmol), then closed and
6076
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© 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 2013, 6069–6077

Phosphane-Phosphite Chelators Built on a α-Cyclodextrin Scaffold
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2011, 12, 429–455.
flushed with nitrogen. CH2Cl2 (5 mL) was added and the autoclave
flushed with H2. The solution was stirred under H2 (5 atm) at
25 °C. After completion of the reaction, the solution was subjected
to filtration through a short silica gel column. Conversion was de-
termined by H NMR spectroscopy. ee values were determined by
GC with CHROMPAK chiral fused silica 25 mϫ0.25 mm Coating
Chirasil-l-Val column.
1
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General Procedure for Hydroformylation Experiments: Hydro-
formylation experiments were carried out in a glass-lined, 100 mL
stainless steel autoclave containing a magnetic stirring bar. In a
typical run, the autoclave was charged under nitrogen with a solu-
tion of preformed rhodium complex 12 (0.002 mmol) in toluene
(1 mL) and toluene (14 mL). Once closed, the autoclave was
flushed twice with syngas (CO/H2, 1:1 v/v), pressurised with 20 bar
of a CO/H2 mixture and heated at 80 °C. After 16 h, the autoclave
was depressurised before styrene (0.57 mL, 0.521 g, 5.0 mmol) and
decane (0.50 mL) were added to the reaction mixture. The auto-
clave was then heated (80 °C) and pressurised (20 bar). The pro-
gress of the reaction was checked by monitoring the pressure de-
crease. During the experiments, several samples were taken and
analysed by gas chromatography.
Supporting Information (see footnote on the first page of this arti-
[10] CD2Cl2 was not used for the VT NMR spectroscopic studies
because of poor solubility of the complexes in this solvent at
low temperature.
1
cle): H, 13C, and 31P NMR spectra are presented.
[11] ROESY spectra performed on both complexes 13 and 14 did
not provide any useful information about the location of the
metal unit with respect to the CD cavity.
[12] G. J. H. Buisman, M. E. Martin, E. J. Vos, A. Klootwijk,
P. C. J. Kamer, P. W. N. M. van Leeuwen, Tetrahedron: Asym-
metry 1995, 6, 719–738.
[13] a) K. Nozaki, N. Sakai, T. Nanno, T. Higashijima, S. Mano,
T. Horiuchi, H. Takaya, J. Am. Chem. Soc. 1997, 119, 4413–
4423; b) K. Nozaki, H. Takaya, T. Hiyama, Top. Catal. 1997,
4, 175–185.
Acknowledgments
The authors are grateful to the Région Alsace and the Centre Inter-
national de Recherche aux Frontières de la Chimie (CIRFC) for
financial support (grant to M. J.).
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Received: June 11, 2013
Published Online: July 30, 2013
Eur. J. Org. Chem. 2013, 6069–6077
© 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
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