Facile one-pot synthesis of BINOL- and H8-BINOL-based aryl phosphites and their use in palladium catalysed asymmetric allylation

Article abstract of DOI:10.1016/j.tet.2005.08.046

Novel P-monodentate aryl phosphite ligands have been synthesised in one step from (R)-BINOL, (R)-H₈-BINOL and (R)-H₈-3,3′- dibromo-BINOL. With the new aryl phosphites, up to 86% ee was observed in the asymmetric Pd-catalysed aminatio

Full text of DOI:10.1016/j.tet.2005.08.046

Tetrahedron 61 (2005) 10514–10520
Facile one-pot synthesis of BINOL- and H8-BINOL-based aryl
phosphites and their use in palladium catalysed
asymmetric allylation
b
a
Konstantin N. Gavrilov,a Sergey E. Lyubimov,b, Pavel V. Petrovskii, Sergey V. Zheglov,
*
Anton S. Safronov,a Roman S. Skazovb and Vadim A. Davankovb
aDepartment of Chemistry, Ryazan State Pedagogic University, 46 Svoboda Street, Ryazan 390000, Russia
bInstitute of Organoelement Compounds, Russian Academy of Sciences, 28 Vavilov Street, 119991 Moscow, Russia
Received 25 May 2005; revised 28 July 2005; accepted 11 August 2005
Available online 29 August 2005
Abstract—Novel P-monodentate aryl phosphite ligands have been synthesised in one step from (R)-BINOL, (R)-H8-BINOL and (R)-H8-3,
30-dibromo-BINOL. With the new aryl phosphites, up to 86% ee was observed in the asymmetric Pd-catalysed amination of 1,3-diphenyl-2-
propenyl acetate with sodium diformylamide. In the enantioselective alkylation of 1,3-diphenyl-2-propenyl acetate with dimethyl malonate,
up to 97% enantioselectivity was achieved.
q 2005 Elsevier Ltd. All rights reserved.
1. Introduction
They proved to be effective stereoselectors in the catalytic
asymmetric Michael addition, aza-Diels–Alder and meso-
epoxide ring opening reactions, synthesis of cyanohydrins,
a-hydroxy- and a-aminophosphonates.1,6 It is also necess-
ary to note that phosphite and phosphoramidite derivatives
of BINOL and H8-BINOL currently represent the most
efficient group of P-monodentate ligands for asymmetric
metal complex catalysis. They showed excellent results in
enantioselective Rh-catalysed hydrogenation, Cu-catalysed
addition of organozinc reagents, Ir-catalysed allylic substi-
tution, Pd-catalysed hydrosilylation-oxidation and Ru-
catalysed hydrogenation of ketones.2,3,7–14 Surprisingly, in
the literature there are no examples of BINOL- and H8-
BINOL-derived phosphites analogous to the compounds
depicted on Figure 1. Previously, we briefly described
synthesis and complexation of ligand 1 with rhodium.15
Developing our project dedicated to application of
P-monodentate phosphite and phosphoramidite derivatives
of BINOL in the Pd-catalysed asymmetric allylation,16,17
herein we report synthesis, complexation and catalytic
properties of phosphites 1 and 2a,b (Schemes 1 and 2)
containing two chiral binaphthyl fragments attached to the
phosphorus atom.
Enantiomeric atropoisomers of 1,10-binaphthyl-2,20-diol
(BINOL), 5,50,6,60,7,70,8,80-octahydro-1,10-binaphthyl-2,
20-diol (H8-BINOL) and their derivatives have been widely
used in both stoichiometric and catalytic asymmetric
organic reactions.1–6 Of special interest are compounds
containing two BINOL or H8-BINOL fragments attached to
a metal atom or heteroatom (Fig. 1).
Figure 1. Compounds containing two chiral binaphthyl fragments attached
to metal atom or heteroatom.
2. Results and discussion
Keywords: P-monodentate phosphite ligands; Asymmetric Pd-catalysed
amination; Enantioselective alkylation.
The new ligands 1 and 2a,b were readily synthesised from
the corresponding binaphthols (Schemes 1 and 2). Notably,
*
Corresponding author. Tel./fax: C7 095 135 6471;
e-mail: lssp452@mail.ru
0040–4020/$ - see front matter q 2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tet.2005.08.046

K. N. Gavrilov et al. / Tetrahedron 61 (2005) 10514–10520
10515
Scheme 1. Synthesis of ligand 1.
Scheme 2. Synthesis of ligands 2a and 2b.
the synthesis does not require obtaining of any intermediate
chlorophosphite or phosphoramidite and proceeds in on
step.
In this case, hydrospirophosphorane 3 was formed instead of
an ‘open-chain’ form 30 (Fig. 3). P(III)-tautomer 30 was
detected neither by 31P NMR nor IR spectroscopy, but
nevertheless phosphorane 3 is able to coordinate to metal
atoms (vide infra).
Compounds 1 and 2a,b are white solids readily soluble in
common organic solvents and stable enough to tolerate
washing with aqueous NaHCO3. A typical shape of narrow
n(OH) absorption bands for 1 and 2a,b (Table 1) and
absence of Dn(OH) in a wide range of concentrations of 1 in
CCl4 solutions indicates intramolecular hydrogen bonding
(Fig. 2).
Table 1. 31P NMR chemical shifts (ppm, CDCl3), IR absorption bands
(cmK1, CHCl3) and cone angles q (degree) of ligands 1–4
Figure 3. Hydrospirophosphorane and its P(III)-tautomer.
Ligand
dP
n(OH)
q
1
145.1
3532
147
154
172
128b
177
Free OH group provides numerous opportunities for
modification of 1 and 2a,b. Thus, trimethylsilylated aryl
phosphite 4 was easily obtained by reaction of 1 with N,O-
bis(trimethylsilyl)acetamide at room temperature
(Scheme 4).
2a
2b
3
138.0 (68%), 138.4 (32%) 3530
139.0 (73%), 143.4 (27%) 3520
K29.3a
144.9
—
—
4
a 1
J
Z836.5 Hz.
P,H
b For ‘open-chain’ form of 3.
To estimate steric demands of ligands 1–4, we calculated
their Tolman’s angles18 by a reported method, namely
semiempirical quantum mechanical AM1 techniques with
full optimisation of geometrical parameters.19 (Table 1).
Calculations showed that steric demands increase in the
1–2a–2b–4 row, ligand 4 being the most bulky (qZ1778)
thanks to its silyl ether group.
Figure 2. Intramolecular hydrogen bonding in the ligand 1.
According to the 31P NMR data (Table 1), partially
hydrogenated compounds 2a,b are represented by two
conformers. A well-known C*-chiral inductor (S,S)-hydro-
benzoin was also directly phosphorylated (Scheme 3).
The electronic demands of the novel ligands were
determined from the 31P NMR and IR spectroscopic data
(Table 2) of their rhodium(I) carbonyl complexes 5, 6a,b
and 7 (Scheme 5).
1
The JP,Rh and n(CO) data for complexes 5, 6a,b indicate
that 1 and 2a,b represent a novel group of highly
p-accepting aryl phosphites. Somewhat lower JP,Rh and
1
n(CO) values of complex 6a in comparison to those of
complex 5 are due to stronger electron donor ability of the
H8-BINOL fragment.3 Increasing of these values in the case
of 6b is caused by the KI effect of bromine atoms.
In contrast to 1 and 2a,b, hydrospirophosphorane 3 does not
Scheme 3. Phosphorylation of the (S,S)-hydrobenzoin.

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K. N. Gavrilov et al. / Tetrahedron 61 (2005) 10514–10520
Scheme 4. Synthesis of the trimethylsilylated aryl phopsphite 4.
Table 2. Selected spectroscopic data for compounds 5, 6a,b, 7 and 8 (in CHCl3)
Compound
31P NMR
1JP,Rh (Hz)
IR, cmK1
dP
n(OH)
n(CO)
n(acac)
5
143.4
137.1
137.3
140.6
138.3
292.5
286.1
299.5
265.2
283.4
3532
3530
3526
3440
3432
2020
2016
2022
1998
2020
1580, 1524
1584, 1524
1581, 1525
1564, 1524
—
6a
6b
7
8
Scheme 5. Synthesis of rhodium(I) carbonyl complexes.
react with [acacRh(CO)2] in CHCl3 at room temperature.
Only after 1 h of refluxing a mixture 3/[acacRh(CO)2] in
toluene, product 7 was detected. According to the 31P NMR
and IR data (Table 2), complex 7 contains an ‘open-chain’
form 30 (Scheme 5). Keeping in mind that [acacRh(CO)2]
reacts with P(III)-ligands immediately and quantitatively,
conclusion can be made that coordination of hydro-
phosphorane 3 is realised by means of oxidative addition.20
Indeed, reaction of 3 with [Rh(CO)2Cl]2, that is able to
dissociate producing the highly reactive in oxidative
addition 14-electron [Rh(CO)2Cl] particles,20 readily pro-
ceeds in CHCl3 at room temperature to afford the dinuclear
rhodium(I) chlorocarbonyl complex 8 (Scheme 5, Table 2).
corresponding reaction solution in CHCl3 (dP 143.5, 143.0,
142.7, 142.5, 127.0, 125.9, 124.9, 10.1 ppm). Pronounced
bulkiness of the aryl phosphite 2b (qZ1728) is the most
probable reason for that. On the contrary, hydrospiro-
phosphorane 3 smoothly formed [Pd(allyl)(30)2]CBF4K
when reacted with 0.5 equiv [Pd(allyl)Cl]2 and 1 equiv
AgBF4 in CHCl3 at room temperature. Immediately after
reaction, only a singlet signal dP 143.9 ppm corresponding
to the [Pd(allyl)(30)2]CBF4K complex was visible in the 31
P
NMR spectrum. But, this product is very unstable, since
already a few minutes later precipitation of a black deposit
was observed and a series of additional signals occurred in
the dP 14–5 ppm region.
Cationic palladium (II) complexes were obtained for the use
in Pd-catalysed allylation (Scheme 6).
Besides, some neutral palladium(II) complexes were
obtained with the aryl phosphite 1, where 1 acted as a
typical P-monodentate ligand (Scheme 7).
Scheme 7. Neutral palladium (II) complexes.
Scheme 6. Cationic palladium (II) complexes.
31P NMR, IR and MS spectroscopic data (see Section 4) are
in a good agreement with the proposed structures for 9 and
10. Signals of both exo and endo isomers of 10 are visible in
its 31P NMR spectra. This is not the case for the complex 9,
due either to fast interconversion of its isomers or to the
absence of one of them (see Ref. 16 and references cited
therein). Unfortunately, an individual [Pd(allyl)(2b)2]CBF4K
complex could not be isolated, for a complicated mixture
of products was observed in the 31P NMR spectrum of the
In particular, the bridge-splitting reaction on the dinuclear
compound [Pd(allyl)Cl]2 with 2 equiv of 1 afforded
complex 11, which represents a mixture of exo and endo
isomers (see Section 4). Significant difference in the
chemical shifts of two terminal allylic carbons (DdcZ
24.3 ppm) indicates a strong trans-influence of the aryl
phosphite 1.21 The interaction between 2 equiv of ligand 1
and [Pd(COD)Cl2] afforded cis palladium complex 12
(Scheme 7). Results of the far-IR spectroscopic studies of

K. N. Gavrilov et al. / Tetrahedron 61 (2005) 10514–10520
10517
Scheme 8. Application of the ligands in asymmetric Pd-catalysed allylic substitution.
solid 12 or its CHCl3 solution (see Section 4) confirm the cis
arrangement of chloride ligands in this complex.22
In allylic amination (Scheme 8), ligands 1 and 2a
afforded up to 61% and 51% ee, correspondingly (L*/
PdZ1:1, Table 4, entries 3 and 6). More bulky aryl
phosphites 2b and 4 gave inferior results (Table 4, entries 9
and 15), while phosphorane 3 provided a nearly racemic
product 15.
The novel ligands 1–4 and their palladium complexes 9 and
10 were tested in the asymmetric Pd-catalysed allylic
substitution (Scheme 8, Tables 3 and 4). Trimethylsilylated
aryl phosphite 4 demonstrated excellent enantioselectivity
in the allylic alkylation of 13 with dimethyl malonate (97%
ee, Table 3, entry 20). Ligand 1 showed an almost equal
enantioselectivity (up to 95% ee) and good conversion
under optimal conditions: L*/PdZ1:1, in CH2Cl2 using
[Pd(allyl)Cl]2 as a precatalyst (Table 3, entries 1–7). In the
case of the partially hydrogenated aryl phosphite 2a, the
highest optical yield was reached with the cationic complex
10 (90%, Table 3, entry 10). Tetrabrominated ligand 2b
afforded only moderate enantioselectivity (up to 63% ee,
Table 3, entries 12 and 13), possibly due to the described
above unselective complexation with palladium(II). Phos-
phorane 3 provided moderate enantioselectivity of up to
56% ee, L*/Pd ratio and applied precatalyst having little
influence on the outcome (Table 3, entries 16–19). Never-
theless, this is the best result in the asymmetric Pd-catalysed
allylic substitution achieved thus far by the use of these
unusual hydrospirophosphorane ligands.23
Taking into account the above discussed results, we tested
the two most efficient aryl phosphites 1 and 2a in the Pd-
catalysed allylic sulfonylation of 1,3-diphenyl-2-propenyl
acetate 13 with sodium para-toluene sulfinate and in the
allylic amination of 13 with sodium diformylamide
(Scheme 8). The type of the nucleophile was found to
play a key role in these processes. Thus, optical purity of the
sulfonylation product 16 obtained by the use of ligand 1 and
its complex 9 did not exceed 24% (R). Under the same
conditions, 2a demonstrated rather good results in both the
[Pd(allyl)Cl]2/4L* (30% yield, 58% ee (S)) and 10 (35%
yield, 65% ee (S)) catalytic systems. On the contrary, in the
allylic amination of 13 with NaN(CHO)2 in THF or CH3CN,
ligand 2a provided no conversion (L*/PdZ1, precatalyst
[Pd(allyl)Cl]2), while the catalytic system [Pd(allyl)Cl]2/
2L* (L*Z1) was rather efficient: 53% yield, 60% ee (R) in
CH3CN and 47% yield, 86% ee (R) in THF.
Table 3. Enantioselective allylic alkylation of 13 with dimethyl malonate
Entry
Catalyst
L*/Pd
Solvent
Conv. (%)
ee (%)
1
2
3
4
5
6
7
8
[Pd(allyl)Cl]2/1
[Pd(allyl)Cl]2/1
[Pd(allyl)Cl]2/1
[Pd(allyl)Cl]2/1
[Pd2(dba)3]!CHCl3/1
[Pd2(dba)3]!CHCl3/1
9
[Pd(allyl)Cl]2/2a
[Pd(allyl)Cl]2/2a
10
1/1
2/1
1/1
2/1
1/1
2/1
2/1
1/1
2/1
2/1
2/1
1/1
2/1
1/1
2/1
1/1
2/1
1/1
2/1
1/1
2/1
THF
THF
11
13
89
93
19
78
99
68
69
50
85
5
14
—
—
76
50
31
32
50
30
49 (R)
18 (R)
95 (R)
78 (R)
39 (S)
43 (S)
86 (R)
71 (R)
52 (R)
90 (R)
81 (R)
48 (R)
63 (R)
—
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
THF
CH2Cl2
CH2Cl2
CH2Cl2
THF
9
10
11
12
13
14
15
16
17
18
19
20
21
10
[Pd(allyl)Cl]2/2b
[Pd(allyl)Cl]2/2b
[Pd(allyl)Cl]2/3
[Pd(allyl)Cl]2/3
[Pd(allyl)Cl]2/3
[Pd(allyl)Cl]2/3
[Pd2(dba)3]!CHCl3/3
[Pd2(dba)3]!CHCl3/3
[Pd(allyl)Cl]2/4
[Pd(allyl)Cl]2/4
THF
—
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
43 (S)
54 (S)
50 (S)
56 (S)
97 (R)
65 (R)

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K. N. Gavrilov et al. / Tetrahedron 61 (2005) 10514–10520
Table 4. Enantioselective allylic amination of 13 with pyrrolidine
Entry
Catalyst
L*/Pd
Solvent
Isolated yield (%)
ee (%)
1
2
3
4
5
6
7
8
[Pd(allyl)Cl]2/1
[Pd(allyl)Cl]2/1
[Pd(allyl)Cl]2/1
[Pd(allyl)Cl]2/1
9
[Pd(allyl)Cl]2/2a
[Pd(allyl)Cl]2/2a
10
[Pd(allyl)Cl]2/2b
[Pd(allyl)Cl]2/2b
[Pd(allyl)Cl]2/3
[Pd(allyl)Cl]2/3
[Pd(allyl)Cl]2/3
[Pd(allyl)Cl]2/3
[Pd(allyl)Cl]2/4
[Pd(allyl)Cl]2/4
1/1
2/1
1/1
2/1
2/1
1/1
1/1
2/1
1/1
1/1
1/1
2/1
1/1
2/1
1/1
2/1
THF
THF
CH2Cl2
CH2Cl2
THF
48
39
57
43
65
68
71
65
56
51
15
8
52 (S)
48 (S)
61 (S)
14 (S)
39 (S)
51 (S)
50 (S)
47 (S)
36 (S)
23 (S)
2 (R)
4 (R)
8 (R)
4 (R)
45 (S)
10 (S)
THF
CH2Cl2
THF
THF
CH2Cl2
THF
THF
CH2Cl2
CH2Cl2
THF
9
10
11
12
13
14
15
16
20
3
45
80
THF
3. Conclusion
diformylamide were prepared as published.28,29 The starting
substrate 13 was synthesised as published.30 (R)-BINOL,
(S,S)-hydrobenzoin, dimethyl malonate, BSA (N,O-bis(tri-
methylsilyl) acetamide) and sodium para-toluene sulfinate
were commercially available.
To conclude, the one-step phosphorylation of (R)-BINOL,
(R)-H8-BINOL and (R)-H8-3,30-dibromo-BINOL with
0.5 equiv of PCl3 results in stable aryl phosphite ligands
bearing two binaphthyl fragments attached to the phos-
phorus atom. Their high catalytic potentials have been
demonstrated by the successful application in asymmetric
Pd-catalysed allylic substitution.
[acacRh(CO)2],31 [Rh(CO)2Cl]2,32 [Pd(allyl)Cl]2,30
[Pd(COD)Cl2]33 and [Pd2(dba)3]$CHCl334 were synthesised
using literature procedures. Rhodium(I) complex 8 was
synthesised for the 31P NMR and IR experiments in
chloroform, analogously to the known procedures.16 The
syntheses of palladium(Ii) complexes 9, 10 and 11 were
performed by techniques similar to that reported.16
4. Experimental
4.1. General
Catalytic experiments: allylic alkylation of substrate 13 with
dimethyl malonate, allylic amination with pyrrolidine,
allylic sulfonylation with sodium para-toluene sulfinate
and allylic amination with NaN(CHO)2 were performed
according to the appropriate procedures.16,17
IR spectra were recorded on a Specord M80 or Nicolet 750
instruments. 31P, 13C, 1H and 29Si NMR spectra were
recorder with a Bruker AMX 400 instrument (162.0 MHz
for 31P, 100.6 MHz for 13C, 400.13 MHz for 1H and
79.46 MHz for 29Si). Complete assignment of all the
resonances in 13C NMR spectra was achieved by the use
of DEPT techniques. Chemical shifts (ppm) are given
relative to Me4Si (1H, 13C and 29Si NMR) and 85% H3PO4
(31P NMR). Mass spectra were recorded with a Varian MAT
311 spectrometer (EI), a Finnigan LCQ Advantage
spectrometer (electrospray ionization technique, ESI), an
MSVKh TOF spectrometer with ionization by Cf-252
fission fragments (plasma desorption technique, PD), a
Varian MAT 731 spectrometer (field desorption technique,
FD). Elemental analyses were performed at the Laboratory
of Microanalysis (Institute of Organoelement Compounds,
Moscow).
4.2. Preparation of ligands 1 and 2a,b. General technique
A solution of PCl3 (0.44 ml, 0.005 mol) in 50 ml of benzene
was added dropwise to a solution of appropriate (R)-
dihydroxybinaphthyl (0.01 mol) and Et3N (2.1 ml,
0.015 mol) in 70 ml of benzene on stirring and cooling to
0 8C. The reaction mixture was then heated for a while to the
boiling point of the solvent, cooled, and filtered; benzene
was removed under reduced pressure (40 Torr), the product
was dried in vacuum (1 Torr, 2 h). Crude 1 and 2a were used
without further purification. Crude 2b was dissolved in
CH2Cl2 (30 ml) and washed with an aqueous saturated
NaHCO3 solution (20 ml). After drying over MgSO4,
filtration and evaporation, the product was dried in vacuum
(1 Torr, 2 h).
Conversion of substrate 1324 and optical purity of products
1424 and 1525 were determined using HPLC (Daicel
Chiralcel OD-H column) as described previously. Optical
yields of product 16 were determined using HPLC ((R,R)-
WHELK-01 column) according to the literature.26 Optical
yields of product 17 were determined using HPLC
(Chiralcel OD column) according to the literature.27
4.2.1. (R)-2-((R)-1,10-binaphthyl-20-hydroxy-2-oxy)-
dinaphtho[2,1-d:10,20-f][1,3,2]dioxaphosphepine (1).
White solid, 2.76 g, (92% yield). 13C NMR (CDCl3): d
111.2, 117.6, 120.5, 121.7, 122.4, 123.9, 124.1, 124.3,
124.8, 125.0, 125.7, 126.1, 126.8, 127.0, 127.1, 127.9,
128.0, 128.2, 129.2, 129.6, 130.0, 130.5, 130.6, 131.1,
132.0, 132.5, 133.3, 134.0, 147.0, 147.2, 148.4, 155.8.
IR, cmK1: n(OH) 3538 (CCl4), 3524 (CH2Cl2), 3516
(nujol). MS (PD), m/z (I, %): 600 (10) [M]C, 585 (21)
All reactions were carried out under a dry argon atmosphere
in freshly dried and distilled solvents; Et3N and pyrrolidine
were twice distilled over KOH and then over a small amount
of LiAlH4 before use. (R)-Br2-H8-BINOL and sodium

K. N. Gavrilov et al. / Tetrahedron 61 (2005) 10514–10520
10519
[MKOCH]C, 315 (81) [MKC20H13O2]C, 268 (100)
[C20H12O]C. MS (FD), m/z (I, %): 600 (100) [M]C, 332
(37) [C20H13O3P]C. MS (ESI), m/z (I, %): 600 (24) [M]C,
585 (20) [MKOCH]C, 315 (16) [MKC20H13O2]C, 268
(100) [C20H12O]C. Anal. Calcd for C40H25O4P: C, 79.99;
H, 4.20; P, 5.16. Found: C, 80.09; H, 4.31; P, 5.04.
132.5, 133.6, 135.0, 146.7, 147.4, 148.3, 152.6. MS (ESI),
m/z (I, %): 673 (3) [M]C, 585 (11) [MKOSiMe3 CH]C,
332 (100) [C20H13O3P]C. Anal. Calcd for C43H33O4PSi: C,
76.77; H, 4.94; P, 4.60. Found: C, 76.59; H, 4.79; P, 4.72.
4.3. Preparation of rhodium complexes 5, 6a,b, 7.
General technique
4.2.2. (R)-2-((R)-5,50,6,60,7,70,8,80-octahydro-1,10-bina-
phthyl-20-hydroxy-2-oxy)-5,50,6,60,7,70,8,80-octahydro-
dinaphtho[2,1-d:10,20-f][1,3,2]dioxaphosphepine (2a).
White solid, 2.87 g, (93% yield). 13C NMR (major
conformer, CDCl3): d 22.7, 22.9, 26.6, 27.4, 29.1, 29.3,
112.7, 117.6, 118.3, 118.6, 119.0, 128.4, 128.6, 129.0,
131.2, 133.1, 134.0, 136.5, 137.3, 145.8, 151.3. MS (EI),
m/z (I, %): 616 (100) [M]C, 340 (80) [C20H21O3P]C, 294
(82) [C20H22O2]C. Anal. Calcd for C40H41O4P: C, 77.90; H,
6.70; P, 5.02. Found: C, 78.11; H, 6.82; P, 5.12.
Rhodium complexes with ligands 1 and 2a,b were
synthesised for the NMR and IR experiments as follows.
A solution of the appropriate ligand (0.1 mmol) in 1 ml of
CHCl3 was added dropwise to a stirred solution of
[acacRh(CO)2] (0.026 g, 0.1 mmol) in 1 ml of the same
solvent. A 1 ml sample of the resulting solution was then
transferred to an NMR tube or IR cuvette and spectral
experiments were carried out. In the case of 3, a solution of
this ligand (0.046 g, 0.1 mmol) and [acacRh(CO)2]
(0.026 g, 0.1 mmol) in 3 ml of toluene was stirred under
reflux for 1 h. Then the solvent was evaporated under
reduced pressure (40 Torr), the residue dissolved in 1 ml of
CHCl3, transferred to an NMR tube or IR cuvette and
spectral experiments were carried out.
4.2.3. (R)-2-((R)-3,30-dibromo-5,50,6,60,7,70,8,80-octa-
hydro-1,10-binaphthyl-20-hydroxy-2-oxy)-3,30-dibromo-
5,50,6,60,7,70,8,80-octahydro-dinaphtho[2,1-d:10,20-f][1,3,
2]dioxaphosphepine (2b). White solid, 3.82 g, (82% yield).
13C NMR (major conformer, CDCl3): d 22.2, 22.5, 26.7,
27.2, 28.6, 28.8, 107.4, 112.5, 123.9, 129.9, 130.1, 131.2,
132.6, 132.7, 133.0, 134.4, 135.2, 136.7, 137.0, 142.3,
143.0, 147.0. MS (ESI), m/z (I, %): 932 (24) [M]C, 852 (49)
[MKBr]C, 498 (22) [C20H19Br2O3P]C, 481 (40) [MK
C20H19Br2O2]C, 451 (100) [C20H19Br2O2]C. Anal. Calcd
for C40H37Br4O4P: C, 51.53; H, 4.00; P, 3.32. Found: C,
51.31; H, 4.11; P, 3.29.
4.4. Cationic palladium complexes
4.4.1. [Pd(allyl)(1)2]C BFK4 (9). White solid, (9 5% yield).
31P NMR (CDCl3): d 142.6 IR, cmK1: n(OH) 3526 (CHCl3).
MS (ESI), m/z (I, %): 1347 (8) [MKBF4]C, 1062 (100)
[MKBF4–C20H13O2]C. Anal. Calcd for C83H55BF4O8P2-
Pd: C, 69.45; H, 3.86; P, 4.32. Found: C, 69.67; H, 3.98; P,
4.22.
4.2.4. Preparation of 2S,3S,7S,8S-tetraphenyl-1,4,6,9-
tetraoxa-5l5-phosphaspiro[4.4]nonane (3). Enantiomeri-
cally pure ligand 3, which was previously reported as a
racemic compound,35 was synthesised according to the
following technique: a solution of P(NEt2)3, (1.37 ml,
0.005 mol) and (S,S)-hydrobenzoin (2.14 g, 0.01 mol) in
25 ml of toluene was stirred under reflux for 1 h. Then all
volatiles were removed in vacuum and the crude product
was purified by recrystallisation from toluene/heptane.
White solid, 1.85 g, (81% yield). 13C NMR (CDCl3): d
79.8, 82.7, 126.6, 126.7, 126.8, 127.7, 128.1, 128.2, 128.3,
128.4, 136.3 (d, JC,PZ9.5 Hz), 137.2 (d, JC,PZ11.8 Hz).
IR, cmK1: n(PH) 2416 (CHCl3). MS (ESI), m/z (I, %): 456
(4) [M]C, 335 (95) [MKC8H9O]C, 260 (100)
[C14H13O3P]C. Anal. Calcd for C28H25O4P: C, 73.67; H,
5.52; P, 6.79. Found: C, 73.61; H, 5.47; P, 6.68.
4.4.2. [Pd(allyl)(2a)2]C BFK4 (10). White solid, (93%
yield). 31P NMR (CDCl3): d 141.4 (54%), 141.2 (46%).
IR, cmK1: n(OH) 3530 (CHCl3). MS (ESI), m/z (I, %): 1381
(46) [MKBF4]C, 1088 (100) [MKBF4–C20H21O2]C. Anal.
Calcd for C83H87BF4O8P2Pd: C, 67.92; H, 5.97; P, 4.22.
Found: C, 67.80; H, 6.11; P, 4.05.
4.5. Neutral palladium complexes
4.5.1. [Pd(allyl)(1)Cl] (11). Light yellow solid, (94% yield).
31P NMR (CDCl3): d 142.8 (71%), 141.9 (29%). 13C NMR
(major isomer, CDCl3): d 57.3 [s, CH2(allyl, trans-Cl)], 81.6
[d, JC,PZ47.4 Hz, CH2(allyl, trans-P)], 112.4, 117.8, 118.0
(br s, CH allyl), 120.2, 121.0, 121.8, 122.9, 123.1, 124.5,
124.9, 125.2, 125.9, 126.7, 126.9, 127.1, 127.3, 127.5,
128.8, 129.1, 129.7, 129.9, 130.1, 130.9, 131.0, 131.4,
131.7, 132.8, 133.6, 133.9, 145.6, 146.7, 146.8, 152.5. IR,
cmK1: n(OH) 3531 (CHCl3); n(Pd–Cl) 282 (nujol). Anal.
Calcd for C43H30ClO4PPd: C, 65.92; H, 3.86; P, 3.95.
Found: C, 65.99; H, 3.80; P, 4.04.
3
3
4.2.5. Preparation of (R)-2-((R)-1,10-binaphthyl-20-tri-
methylsilanoxy-2-oxy)-dinaphtho[2,1-d:10,20-f][1,3,2]
dioxaphosphepine (4). Ligand 4 was synthesised according
to the known technique:36 a solution of 1 (0.3 g, 0.5 mmol)
and BSA (0.38 ml, 1.5 mmol) in 3 ml of CHCl3 was stirred
at room temperature for 1 h. Then the mixture was
concentrated under reduced pressure (40 Torr), the residue
washed with hexane and dried in vacuum (1 Torr, 3 h) at
60 8C. White solid, 0.3 g, (90% yield). 1H NMR (CDCl3): d
0.09 (9H, s), 6.54 (1H, d, JH,HZ8.0 Hz), 7.23 (10H, m), 7.37
4.5.2. Preparation of cis-[Pd(1)2Cl2] (12). A solution of 1
(0.12 g, 0.2 mmol) in 5 ml of CHCl3 was added dropwise to
a stirred solution of [Pd(COD)Cl2] (0.029 g, 0.1 mmol) in
5 ml of the same solvent. The resulting solution was stirred
for 1 h and concentrated to 1 ml under reduced pressure
(40 Torr). The product was precipitated with hexane–ether
(2/1), thoroughly washed three times with ether to remove
cycloocta-1,5-diene and dried in vacuum (1 Torr, 1 h).
Yellow solid, (91% yield). 31P NMR (CDCl3): d 105.5. IR,
cmK1: n(OH) 3519 (CHCl3); n(Pd–Cl) 338, 304 (CHCl3),
(5H, m), 7.53 (1H, d, JH,HZ9.9 Hz), 7.73 (1H, d, JH,H
Z
9.9 Hz), 7.87 (6H, m). 13C NMR (CDCl3): d 1.8, 111.4,
117.8, 120.1, 120.7, 122.5, 123.9, 124.6, 124.1, 124.9,
125.3, 125.7, 126.4, 126.6, 127.0, 127.3, 128.1, 128.5,
128.7, 129.2, 129.9, 130.1, 130.5, 130.6, 131.7, 132.2,

10520
K. N. Gavrilov et al. / Tetrahedron 61 (2005) 10514–10520
15. Gavrilov, K. N.; Mikhel, I. S. Russ. J. Inorg. Chem. 1994, 39,
439.
335, 304 (nujol). MS (ESI), m/z (I, %): 1306 (29) [MK
2Cl]C, 1092 (100) [MKC20H13O2]C. Anal. Calcd for
C80H50Cl2O8P2Pd: C, 69.70; H, 3.66; P, 4.49. Found: C,
69.92; H, 3.74; P, 4.32.
16. Tsarev, V. N.; Lyubimov, S. E.; Shiryaev, A. A.; Zheglov,
S. V.; Bondarev, O. G.; Davankov, V. A.; Kabro, A. A.;
Moiseev, S. K.; Kalinin, V. N.; Gavrilov, K. N. Eur. J. Org.
Chem. 2004, 2214.
Acknowledgements
17. Gavrilov, K. N.; Lyubimov, S. E.; Zheglov, S. V.; Benetsky,
E. B.; Davankov, V. A. J. Mol. Catal. A: Chem. 2005, 231,
255.
The authors thank Dr. A.V. Korostylev (Leibniz-Institut fu¨r
¨
Organische Katalyse an der Universitat Rostock, Germany)
for his assistance in preparation of the manuscript and Prof.
18. Tolman, C. A. Chem. Rev. 1977, 77, 313.
19. Polosukhin, A. I.; Kovalevskii, A. Y.; Gavrilov, K. N. Russ.
J. Coord. Chem. 1999, 25, 758.
¨
A. Borner (Leibniz-Institut fur Organische Katalyse an der
Universitat Rostock, Germany) for a generous gift of H8-
¨
¨
20. Gavrilov, K. N.; Korostylev, A. V.; Polosukhin, A. I.;
Bondarev, O. G.; Kovalevskii, A. Y.; Davankov, V. A.
J. Organomet. Chem. 2000, 613, 148.
BINOL. The authors gratefully acknowledge receiving the
chiral HPLC columns (R,R) WHELK-01 from Regis
Technologies (USA) and Chiralcel OD-H from Daicel
Chemical Industries, Ltd (Japan). This work was partially
supported by the Russian Foundation for Basic Research
(Grant no 03-03-32181) and Grant of the President of RF for
young scientists—doctors of sciences (No. MD-21.2003.03).
Financial support from the Russian Science Support
Foundation is gratefully acknowledged.
21. Kumar, P. G. A.; Dotta, P.; Hermatschweiler, R.; Pregosin,
P. S. Organometallics 2005, 24, 1306.
22. Mikhel, I. S.; Gavrilov, K. N.; Polosukhin, A. I.; Rebrov, A. I.
Russ. Chem. Bull. 1998, 47, 1585.
23. Gavrilov, K. N.; Polosukhin, A. I.; Bondarev, O. G.;
Lyubimov, S. E.; Lyssenko, K. A.; Petrovskii, P. V.;
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25. Smyth, D.; Tye, H.; Eldred, C.; Alcock, N. W.; Wills, M.
J. Chem. Soc., Perkin Trans. 1 2001, 2840.
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