Diastereomeric P,N-bidentate amidophosphites based on (S,S)- and (R,R)-hydrobenzoin as ligands in the Pd-catalyzed asymmetric allylation

Article abstract of DOI:10.1007/s11172-011-0314-5

New P, N-bidentate diastereomeric amidophosphite ligands were obtained by phosphorylation of (S)-2-[(phenylamino)methyl]pyrrolidine involving (4S,5S)- and (4R,5R)-2-chloro-4,5-diphenyl-1,3,2-dioxaphospholanes. Their efficiency in the Pd-catalyzed enantios

Full text of DOI:10.1007/s11172-011-0314-5

Russian Chemical Bulletin, International Edition, Vol. 60, No. 10, pp. 2063—2067, October, 2011
2063
Diastereomeric P,Nꢀbidentate amidophosphites based
on (S,S)ꢀ and (R,R)ꢀhydrobenzoin as ligands in the Pdꢀcatalyzed
asymmetric allylation
K. N. Gavrilov,a I. V. Chuchelkin,a S. V. Zheglov,a N. N. Groshkin,a I. M. Novikov,a
E. A. Rastorguev,b and V. A. Davankovb
aS. A. Esenin Ryazan State University,
46 ul. Svobody, 390000 Ryazan, Russian Federation.
Fax: +7 (491) 228 1435. Eꢀmail: k.gavrilov@rsu.edu.ru
bA. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences,
28 ul. Vavilova, 119991 Moscow, Russian Federation.
Fax: +7 (499) 135 6471. Eꢀmail: hagehoge@mail.ru
New P,Nꢀbidentate diastereomeric amidophosphite ligands were obtained by phosphorylaꢀ
tion of (S)ꢀ2ꢀ[(phenylamino)methyl]pyrrolidine involving (4S,5S)ꢀ and (4R,5R)ꢀ2ꢀchloroꢀ4,5ꢀ
diphenylꢀ1,3,2ꢀdioxaphospholanes. Their efficiency in the Pdꢀcatalyzed enantioselective allylic
substitution was compared, it was found that the reaction involving (E)ꢀ1,3ꢀdiphenylallyl aceꢀ
tate and pyrrolidine gives up to 75% ee.
Key words: amidophosphites, 1,3,2ꢀdioxaphospholanes, palladium catalysts, asymmetric
allylation.
A fast progress in the asymmetric metal complex caꢀ
talysis is of fundamental and practical importance. From
the one hand, this implies obtaining new knowledge on
the nature of molecular chiral identification and asymꢀ
metric induction. From the other hand, this means develꢀ
opment of highly efficient methods for the preparation of
enantiopure drugs, pheromones, agrochemicals, food adꢀ
ditives, fragrances, and stereoindividual polymers. In adꢀ
dition, the use of highly selective catalytic systems is one
of the basic principles of "green chemistry".1—5 Activity
and stereoselectivity of the metal complex catalysts is
largely defined by successful strategy of the design and
synthesis of the corresponding chiral ligands, in the first
place, phosphorusꢀcontaining ones.6,7. Virtually all the
arsenal of available natural compounds, as well as binaphꢀ
thyl, biphenyl, and ferrocene derivatives, were used in the
preparation of large libraries of different phosphorusꢀconꢀ
taining chiral ligands. Nevertheless, the overwhelming
majority of such ligands in the composition of the correꢀ
sponding metal complexes are able to catalyze with differꢀ
ent enantioselectivity either a certain type of chemical
transformations, or one certain reaction. The versatile
enough (the soꢀcalled "privileged") ligands are very rare,
and their expensiveness significantly restrains their wide
practical use. In this connection, development of simple
and efficient methods for the preparation of inexpensive
ligands based on available optically pure synthons is still a
relevant problem.8—11
Ligands of the phosphite nature are of the first and
foremost interest, since they advantageously differ in synꢀ
thetic availability, stability to oxidation, pronounced
πꢀacidity, and are inexpensive. This allows one to easy
enough obtain wide series of ligands, including applicaꢀ
tion of parallel and solidꢀphase syntheses.11—17
Introduction of additional donor atom, for example,
a nitrogen atom, into the structure of the phosphorusꢀ
containing chiral ligand creates new possibilities. In this
case, enantioselectivity of the catalyst is contributed not
only by stereochemistry of the ligand, but also by its elecꢀ
tron asymmetry due to the presence of the donor atoms of
different nature. Electron asymmetry greatly affects the
mechanism of the catalytic cycle, and, as a consequence,
efficiency of the chirality transfer in its key step. Thus, the
πꢀacceptor character of the phosphorus atom in the P,Nꢀbiꢀ
dentate ligands allows one to stabilize the low oxidation
states of the complexation metals and increase their electroꢀ
philicity, whereas the σꢀdonor ability of the nitrogen atom
make them more susceptible to the processes of oxidative
addition. Different transꢀeffects of the phosphorus and
nitrogen donor centers are also significant factors.18—20
In the present work, we report on obtaining and appliꢀ
cation in enantioselective catalysis of new P,Nꢀbidentate
amidophosphites (S,S,S)ꢀ3 and (R,R,S)ꢀ3 containing
1,3,2ꢀdioxaphospholane rings based on the (S,S)ꢀ and
(R,R)ꢀhydrobenzoin. Note that this synthon is one of the
most available C2ꢀsymmetric enantiopure diols.21 It should
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 2026—2030, October, 2011.
1066ꢀ5285/11/6010ꢀ2063 © 2011 Springer Science+Business Media, Inc.

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Gavrilov et al.
Scheme 1
be noted that several Pꢀmonodentate and P,Pꢀbidentate
phosphites of the 1,3,2ꢀdioxaphospholane series based on
hydrobenzoin were used in the Cuꢀcatalyzed conjugated
addition, Rhꢀcatalyzed hydroformylation, and Niꢀcataꢀ
lyzed hydrovinylation with low or moderate enantioselecꢀ
tivity (no more than 60% ee).22—25 We have chosen
Pdꢀcatalyzed asymmetric allylation as a catalytic process
for the testing the amidophosphites (S,S,S)ꢀ3 and (R,R,S)ꢀ3,
which is used for both the evaluation of efficiency of new
chiral ligands and stereoselective synthesis of valuable natꢀ
ural compounds.26—29 It should be noted that earlier we
have suggested several efficient P*,Nꢀbidentate ligands of
the phosphite nature bearing asymmetric phosphorus atꢀ
oms for a number of Pdꢀcatalyzed asymmetric allylation
reactions.30—32
Results and Discussion
The new P,Nꢀbidentate amidophosphites (S,S,S)ꢀ3
and (R,R,S)ꢀ3 were synthesized by phosphorylation of
(S)ꢀ2ꢀ[(phenylamino)methyl]pyrrolidine (1) with the reꢀ
actants (S,S)ꢀ2 and (R,R)ꢀ2 in toluene (Scheme 1). It is
very important that the starting enantiopure diamine 1 is
easy available, since it can be obtained by the condensaꢀ
tion of (S)ꢀglutamic acid and aniline with subsequent hyꢀ
dride reduction of the (S)ꢀpyroglutamic acid anilide that
formed.33,34 It is necessary to note that the known method
for the preparation of enantiomeric phosphorylating agents
(S,S)ꢀ2 and (R,R)ꢀ2 consists in the reflux of a suspension
of (S,S)ꢀ or (R,R)ꢀhydrobenzoin in excess PCl3 for a long
time (about 10—12 h).35 We improved this method and
carried out the reaction in the presence of Nꢀmethylpyrꢀ
rolidone in catalytic amount, which was used earlier for
the preparation of chlorophosphite based on BINOL (see
Ref. 36). This allowed us to reduce the reaction time to
20 min, thus developing an efficient procedure for the
synthesis of amidophosphites (S,S)ꢀ2 and (R,R)ꢀ2.
the 13C NMR spectra. Besides, treatment of compound 1
with two equivalents of (S,S)ꢀ2 under conditions similar
to those in the synthesis of ligand (S,S,S)ꢀ3 (see Experiꢀ
mental) does not lead to phosphorylation of this diamine
at both amino groups with the formation of the correꢀ
sponding P,Pꢀbidentate derivative. Instead, the 31P NMR
spectrum of the residue after filtration and concentration
of the reaction solution exhibits the signals for the phosꢀ
phorylating reactant (S,S)ꢀ2 present in excess at δP 174.2
and for the product (S,S,S)ꢀ3 at δP 144.4 (CDCl3).
Amidophosphites (S,S,S)ꢀ3 and (R,R,S)ꢀ3 were isoꢀ
lated by flashꢀchromatography, they are well soluble in
most organic solvents and are stable enough in air and on
prolonged storage under dry atmosphere.
It should be emphasized that a direct phosphorylation
of 1 upon the action of (S,S)ꢀ2 or (R,R)ꢀ2 occurs excluꢀ
The ligands (S,S,S)ꢀ3 and (R,R,S)ꢀ3 (L) were studied
in the Pdꢀcatalyzed asymmetric allylation with (E)ꢀ1,3ꢀdiꢀ
phenylallyl acetate (4), [Pd(allyl)Cl]2 was chosen as a preꢀ
catalyst (Scheme 2, Table 1—3). In the allylation of pyrꢀ
rolidine with compound 4, palladium complexes of both
diastereomeric ligands provide the quantitative converꢀ
sion, but diverse asymmetric induction. Amidophosphite
(S,S,S)ꢀ3 virtually irrespective of the solvent nature and
the molar ratio L : Pd leads to the product (R)ꢀ5 with low
enantioselectivity (no more than 29% ee, see Table 1, enꢀ
tries 1—4). Conversely, when the ligand (R,R,S)ꢀ3 is inꢀ
volved the amine (R)ꢀ5 is formed with the enantiomeric
excess up to 75% (see Table 1, entries 5—8). Consequentꢀ
ly, in the case of (R,R,S)ꢀ3, a concerted stereoselective
action of its (R,R)ꢀhydrobenzoin and (S)ꢀ2ꢀ[(phenylꢀ
amino)methyl]pyrrolidine fragments takes place. The
highest enantioselectivity is observed when the reaction is
carried out in THF with the molar ratio L : Pd = 2 (see
1
sively at the pyrrolidine amino group. The 31P, H, and
13C NMR spectroscopic data for compounds (S,S,S)ꢀ3
and (R,R,S)ꢀ3 completely agree with the structure sugꢀ
gested for them (see Experimental). Note, in particular,
the presence of signals characteristic of the protons of the
peripheral aniline NH group as broad singlets at δH 4.25
and 4.22, respectively,33,37 in their 1H NMR spectra. The
IR spectra of solutions of amidophosphites (S,S,S)ꢀ3 and
(R,R,S)ꢀ3 in CHCl3 exhibit symmetric absorption bands
of medium intensity ν(N—H) 3368 and 3381 cm–1 also
corresponding to the secondary NH(Ph) amino group.38
In addition, unlike the signals for the carbon atoms in the
phenyl substituent at the aniline nitrogen atom, the sigꢀ
nals for the carbon atoms of the pyrrolidine fragment in
the molecules of (S,S,S)ꢀ3 and (R,R,S)ꢀ3 are characterꢀ
ized by the spinꢀspin coupling constants 2JC,P and 3JC,P in

Diastereomeric P,Nꢀbidentate amidophosphites
Russ.Chem.Bull., Int.Ed., Vol. 60, No. 10, October, 2011
2065
Table 2. The Pdꢀcatalyzed allylation of dipropylamine with
diphenylallyl acetate 4a
Table 1, entry 6). Note that an increase in the molar ratio
L : Pd leads to the increase in enantioselectivity in THF
and to its decrease in CH2Cl2 (see Table 1, cf. pairs of
entries 5, 6 and 7, 8).
Entry
Ligand
L/Pd Solvent
Converꢀ
sion (%)
ee (%)b
1
2
3
4
5
6
7
8
(S,S,S)ꢀ3
(S,S,S)ꢀ3
(S,S,S)ꢀ3
(S,S,S)ꢀ3
(R,R,S)ꢀ3
(R,R,S)ꢀ3
(R,R,S)ꢀ3
(R,R,S)ꢀ3
1
2
1
2
1
2
1
2
THF
THF
CH2Cl2
CH2Cl2
THF
THF
CH2Cl2
CH2Cl2
82
89
11 (–)
9 (–)
7 (–)
13 (–)
65 (+)
55 (+)
23 (+)
15 (+)
Scheme 2
100
100
100
100
100
100
a Reaction conditions: [Pd(allyl)Cl]2 (2 mol.%), 20 °C, 48 h.
b Conversion of 4 and enantiomeric excess of product 6 were
determined by HPLC (a Daicel Chiralcel OD—H chiral stationꢀ
ary phase, the eluent C6H14 : PriOH : HNEt2 = 1000 : 1 : 1 was
used at the rate 0.4 mL min–1, detection at 254 nm, the retention
times: for (+)ꢀisomer 8.2 min, for (–)ꢀisomer 9.1 min). The sign
of the optical rotation angle is shown in parentheses.
(E)ꢀ1,3ꢀdiphenylallyl acetate (4) (Table 3). In contrast to
the reactions involving amines, the better results were
shown by the diastereomer (S,S,S)ꢀ3: the product (R)ꢀ7 is
formed with the enantioselectivity up to 60% ee at high
conversions of the starting substrate 4 (see Table 3, entries
1—4). The optimum solvent is THF at the molar ratio
L : Pd = 2 (see Table 3, entry 2). The allylic substitution
involving allyl acetate 4 and amidophosphite (R,R,S)ꢀ3
proceeds with lower conversion and enantioselectivity (to
45% ee, see Table 3, entries 5—8), with the product 7
having the (S)ꢀconfiguration.
BSA is the bisꢀtrimethylsilylacetamide, cat is the catalyst.
When dipropylamine is used as the Nꢀnucleophile,
amidophosphite (R,R,S)ꢀ3 is also more efficient ligand
allowing us to reach the complete conversion of the subꢀ
strate 4 and enantioselectivity up to 65% ee (Table 2).
As in the allylation of pyrrolidine, the higher asymꢀ
metric induction is reached in THF, but at the molar ratio
L : Pd = 1 (see Table 2, entry 5). The diastereomeric ligand
(S,S,S)ꢀ3 allows one to obtain the opposite enantiomer of
amine 6, but with low (7—13% ee) enantioselectivity (see
Table 2, entries 1—4).
In conclusion, in the present work we obtained the
first representatives of P,Nꢀbidentate ligands of the phosꢀ
phite nature based on the known C2ꢀsymmetric enanꢀ
tiopure 1,2ꢀdiol, viz., hydrobenzoin. A convenient method
The P,Nꢀbidentate ligands (S,S,S)ꢀ3 and ((R,R,S)ꢀ3
were also used in the allylation of dimethyl malonate with
Table 1. The Pdꢀcatalyzed allylation of pyrrolidine with dipheꢀ
nylallyl acetate 4a
Table 3. The Pdꢀcatalyzed allylation of dimethyl malonate with
diphenylallyl acetate 4a
Entry Ligand
L/Pd Solꢀ
vent
Converꢀ
sion (%) (configuration)
ee (%)b
Entry Ligand
L/Pd Solvent
Converꢀ
sion (%) (configuration)
ee (%)b
1
2
3
4
5
6
7
8
(S,S,S)ꢀ3
(S,S,S)ꢀ3
(S,S,S)ꢀ3
(S,S,S)ꢀ3
(R,R,S)ꢀ3
(R,R,S)ꢀ3
(R,R,S)ꢀ3
(R,R,S)ꢀ3
1
2
1
2
1
2
1
2
THF
THF
CH2Cl2
CH2Cl2
THF
THF
CH2Cl2
CH2Cl2
100
95
19 (R)
21 (R)
29 (R)
23 (R)
63 (R)
75 (R)
65 (R)
57 (R)
1
2
3
4
5
6
7
8
(S,S,S)ꢀ3
1
2
1
2
1
2
1
2
THF
THF
CH2Cl2
CH2Cl2
THF
THF
CH2Cl2
CH2Cl2
89
100
100
97
62
66
30 (R)
60 (R)
20 (R)
19 (R)
11 (S)
10 (S)
13 (S)
45 (S)
(S,S,S)ꢀ3
(S,S,S)ꢀ3
(S,S,S)ꢀ3
(R,R,S)ꢀ3
(R,R,S)ꢀ3
(R,R,S)ꢀ3
(R,R,S)ꢀ3
100
100
100
100
100
100
100
100
a Reaction conditions: [Pd(allyl)Cl]2 (2 mol.%), 20 °C, 48 h.
b Conversion of 4 and enantiomeric excess of product 5 were
determined by HPLC (a Daicel Chiralcel OD—H chiral staꢀ
tionary phase, the eluent C6H14 : PriOH : HNEt2 = 200 : 1 : 0.1
was used at the rate 0.9 mL min–1, detection at 254 nm).
a Reaction conditions: [Pd(allyl)Cl]2 (2 mol.%), 20 °C, 48 h.
b Conversion of 4 and enantiomeric excess of product 7 were
determined by HPLC (a Daicel Chiralcel OD—H chiral stationꢀ
ary phase, the eluent C6H14 : PriOH = 99 : 1 was used at the rate
0.6 mL min–1, detection at 254 nm).

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Gavrilov et al.
moved by filtration, the filtrate was concentrated in vacuo
(40 Torr). The products (S,S,S)ꢀ3 and (R,R,S)ꢀ3 were purified
by flashꢀchromatography on alumina using hexane—ethyl aceꢀ
tate (1 : 1) as an eluent.
was used for the synthesis of available diastereomeric
amidophosphites (S,S,S)ꢀ3 and (R,R,S)ꢀ3 with the secꢀ
ondary peripheral amino group, which is based on the
efficient procedure for the preparation of chlorophosphites
from (S,S)ꢀ and (R,R)ꢀhydrobenzoins as necessary phosꢀ
phorylating agents. A model reactions of the Pdꢀcatalyzed
asymmetric allylation using (E)ꢀ1,3ꢀdiphenylallyl acetate (4)
demonstrated that (S,S,S)ꢀ3 and (R,R,S)ꢀ3 are the comꢀ
plementary chiral ligands. Allylation of pyrrolidine showed
a good level of enantioselectivity up to 75% ee.
(4S,5S)ꢀDiphenylꢀ2ꢀ[(S)ꢀ(2´ꢀ[(phenylamino)methyl]pyrꢀ
rolidinꢀ1´ꢀyl)]ꢀ1,3,2ꢀdioxaphospholane ((S,S,S)ꢀ3). The yield
was 1.11 g (78%), colorless viscous oil. Found (%): C, 72.0;
H, 6.59; N, 6.65. C25H27N2O2P. Calculated (%): C, 71.75;
H, 6.50; N, 6.69. 31P NMR (CDCl3), δ: 144.4. 13C NMR (CDCl3),
δ (JC,P): 24.9 (s, CH2), 29.9 (d, CH2, 3J = 4.0 Hz); 44.5 (d, CH2N,
2J = 9.0 Hz); 48.4 (d, CH2N, 3J = 4.8 Hz); 56.9 (d, CHN,
2J = 24.9 Hz); 83.4 (d, CHO, 2J = 10.0 Hz); 85.2 (d, CHO,
2J = 8.9 Hz); 113.0 (s, CHPhNH); 117.3 (s, CHPhNH); 126.5
(s, CHPh); 127.1 (s, CHPh); 128.4 (s, CHPh); 128.5 (s, CHPh);
128.6 (s, CHPh Hz); 129.2 (s, CHPhNH); 136.7 (d, CPh, 3J = 5.0 Hz);
Experimental
31
P, 1H, and 13C NMR spectra were recorded on a Bruker
137.6 (d, CPh,
3J = 10.1 Hz); 148.1 (s, CPhNH). 1H NMR
Avance 400 spectrometer (161.98, 400.13, and 100.61 MHz, reꢀ
spectively) relatively to 85% H3PO4 in D2O (31P) and Me4Si
(1H and 13C). Signals in the 13C NMR spectra were assigned
using the DEPT procedure. Mass spectra with the laser desorpꢀ
tion ionization (MALDI TOF/TOF) were recorded on a Bruker
Daltonics Ultraflex instrument. IR spectra were recorded on
a Specord Mꢀ80 spectrometer in CHCl3 in polyethylene cuvettes.
Optical rotation was measured on a Perkin—Elmer 341 polariꢀ
meter. Enantiomeric analysis of products of the catalytic reacꢀ
tions was performed on a HP Agilent 1100 HPLꢀchromatograph.
Elemental analysis was performed in the Laboratory of Organic
Microanalysis of INEOS RAS.
All the reactions were carried out under dry argon in anhyꢀ
drous solvents. The starting compounds, i.e., the [Pd(allyl)Cl]2
complex and (E)ꢀ1,3ꢀdiphenylallyl acetate (4), were synthesized
according to the known procedures.39 Catalytic experiments on
asymmetric allylation of pyrrolidine, dipropylamine, and diꢀ
methyl malonate upon the action of 4, determination of converꢀ
sion of 4 and enantiomeric excess of products 5, 6, and 7 were
carried out according to the published procedures.40—42
(S)ꢀGlutamic acid, (S,S)ꢀhydrobenzoin, (R,R)ꢀhydrobenzꢀ
oin, Nꢀmethylpyrrolidone, pyrrolidine, dipropylamine, as well
as dimethyl malonate and bisꢀtrimethylsilylacetamide (BSA)
were commercially available reactants from Fluka and Aldrich.
Synthesis of enantiomeric phosphorylating agents (S,S)ꢀ2 and
(R,R)ꢀ2 (general procedure). NꢀMethylpyrrolidone (0.01 g,
0.1 mmol) was added to a suspension of (S,S)ꢀhydrobenzoin or
(R,R)ꢀhydrobenzoin (0.75 g, 3.5 mmol) in PCl3 (4 mL,
45.5 mmol) and the mixture was refluxed for 20 min until the
complete homogenization was reached. Then the excess of PCl3
was removed in vacuo (40 Torr), the residue was dried in vacuo
(30 min, 1 Torr) to remove the PCl3 traces. The yield was 0.96 g
(98%), pale yellow solid compound. Spectral and physicochemꢀ
ical characteristics of enantiomeric products (S,S)ꢀ2 and (R,R)ꢀ2
completely agree with the data published earlier.35
Synthesis of P,Nꢀbidentate ligands (S,S,S)ꢀ3 and (R,R,S)ꢀ3
(general procedure). A solution of (S)ꢀ2ꢀ[(phenylamino)methyl]ꢀ
pyrrolidine (1) (0.6 g, 3.4 mmol) in toluene (5 mL) was added
dropwise to a solution of (4S,5S)ꢀ2ꢀchloroꢀ4,5ꢀdiphenylꢀ1,3,2ꢀ
dioxaphospholane ((S,S)ꢀ2) or (4R,5R)ꢀ2ꢀchloroꢀ4,5ꢀdiphenylꢀ
1,3,2ꢀdioxaphospholane ((R,R)ꢀ2) (0.95 g, 3.4 mmol) and Et3N
(1.22 mL, 8.8 mmol) in toluene (15 mL) over 20 min at 20 °C
with vigorous stirring. The mixture that obtained was stirred for
24 h at 20 °C, then heated to 40 °C, stirred at this temperature for
1 h, and cooled to 20 °C. A precipitate of Et3N•HCl was reꢀ
(CDCl3), δ: 1.78 (m, 1 H); 1.94 (m, 2 H); 2.04 (m, 1 H); 3.07
(m, 1 H); 3.14 (m, 1 H); 3.39 (m, 1 H); 3.55 (m, 1 H); 4.15 (m, 1 H);
4.25 (br.s, 1 H); 4.89(dd, 2 H, 3J = 8.0 Hz); 6.62 (d, 2 H,
3J = 7.9 Hz); 6.68 (t, 1 H, 3J = 7.9 Hz); 7.15 (t, 2 H, 3J = 7.9 Hz);
7.25 (m, 10 H). MS (MALDI TOF/TOF), m/z (Irel (%)): 419
[M + H]+ (21), 283 [OCHPhCHPhOPH + K]+ (100).
(4R,5R)ꢀDiphenylꢀ2ꢀ[(S)ꢀ(2´ꢀ[(phenylamino)methyl]pyrrolꢀ
idinꢀ1´ꢀyl)]ꢀ1,3,2ꢀdioxaphospholane ((R,R,S)ꢀ3). The yield was
1.02 g (72%), colorless viscous oil. Found (%): C, 71.89; H, 6.47;
N, 6.75. C25H27N2O2P. Calculated (%): C, 71.75; H, 6.50;
N, 6.69. 31P NMR (CDCl3), δ: 142.8. 13C NMR (CDCl3), δ,
(JC,P): 24.7 (s, CH2); 29.5 (d, CH2, 3J = 3.0 Hz); 44.1 (d, CH2N,
2J = 3.9 Hz), 48.3 (d, CH2N, 3J = 3.1 Hz); 57.1 (d, CHN,
2J = 20.2 Hz); 82.7 (d, CHO, 2J = 7.0 Hz); 85.1 (d, CHO,
2J = 4.9 Hz); 112.7 (s, CHPhNH); 117.1 (s, CHPhNH); 126.5
(s, CHPh); 127.0 (s, CHPh); 128.2 (s, CHPh); 128.3 (s, CHPh);
128.4 (s, CHPh); 129.0 (s, CHPhNH); 135.8 (d, CPh); 137.1
3
1
(d, CPh, J = 7.1 Hz); 147.8 (s, CPhNH). H NMR (CDCl3), δ:
1.77 (m, 1 H); 1.94 (m, 2 H); 2.05 (m, 1 H); 3.13 (m, 2 H); 3.24
(m, 1 H); 3.76 (m, 1 H); 4.12 (m, 1 H); 4.22 (br.s, 1 H);
4.87(dd, 2 H, 3J = 8.0 Hz); 6.62 (d, 2 H, 3J = 8.0 Hz); 6.70
(t, 1 H, 3J = 8.0 Hz); 7.17 (t, 2 H, 3J = 8.0 Hz); 7.28 (m, 10 H).
MS (MALDI TOF/TOF), m/z (Irel (%)): 419 [M + H]+ (31),
283 [OCHPhCHPhOPH + K]+ (100).
Asymmetric allylation of pyrrolidine with (E)ꢀ1,3ꢀdiphenylalꢀ
lyl acetate (4) (general procedure). A solution of [Pd(allyl)Cl]2
(0.0037 g, 0.01 mmol) and the corresponding ligand (0.02 mmol
or 0.04 mmol) in the corresponding solvent (5 mL) was stirred
for 40 min (see Table 1). Then, (E)ꢀ1,3ꢀdiphenylallyl acetate
(0.1 mL, 0.5 mmol) was added and the solution was stirred for
another 15 min, followed by addition of freshly distilled pyrrolꢀ
idine (0.12 mL, 1.5 mmol). The reaction mixture was stirred for
48 h, diluted with hexane (5 mL), and filtered through the layer
of celite. The solvents were evaporated at reduced pressure
(40 Torr), the residue was dried in vacuo (10 Torr). Conversion
of the substrate 4 and enantiomeric excess of the product 5 were
determined by HPLC on a chiral stationary phase.
Asymmetric allylation of dipropylamine with (E)ꢀ1,3ꢀdiphenylꢀ
allyl acetate (4) (general procedure). A solution of [Pd(allyl)Cl]2
(0.0037 g, 0.01 mmol) and the corresponding ligand (0.02 mmol
or 0.04 mmol) in the corresponding solvent (5 mL) was stirred
for 40 min (see Table 2), followed by addition of (E)ꢀ1,3ꢀdiꢀ
phenylallyl acetate (0.1 mL, 0.5 mmol). After the solution was
stirred for another 15 min, freshly distilled dipropylamine
(0.15 mL, 1.5 mmol) was added. The reaction mixture was stirred

Diastereomeric P,Nꢀbidentate amidophosphites
Russ.Chem.Bull., Int.Ed., Vol. 60, No. 10, October, 2011
2067
for 48 h, diluted with hexane (5 mL), and filtered through the
layer of celite. The solvents were evaporated at reduced pressure
(40 Torr), the residue was dried in vacuo (10 Torr). Conversion
of the substrate 4 and enantiomeric excess of the product 6 were
determined by HPLC on a chiral stationary phase.
17. B. H. G. Swennenhuis, R. Chen, P. W. N. M. van Leeuwen,
J. G. de Vries, P. C. J. Kamer, Eur. J. Org. Chem., 2009, 5796.
18. K. N. Gavrilov, A. I. Polosukhin, Usp. Khim., 2000, 69, 721
[Russ. Chem. Rev. (Engl. Transl.), 2000, 69, 661].
19. G. Chelucci, G. Orru, G. A. Pinna, Tetrahedron, 2003,
59, 9471.
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21. K. C. Bhowmick, N. N. Joshi, Tetrahedron: Asymmetry, 2006,
17, 1901.
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Asymmetry, 1997, 8, 3193.
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1998, 9, 329.
Asymmetric allylation of dimethyl malonate with (E)ꢀ1,3ꢀdiꢀ
phenylallyl acetate (4) (general procedure). A solution of
[Pd(allyl)Cl]2 (0.0037 g, 0.01 mmol) and the corresponding
ligand (0.02 mmol or 0.04 mmol) in the corresponding solvent
(5 mL) was stirred for 40 min (see Table 3), followed by addition
of (E)ꢀ1,3ꢀdiphenylallyl acetate (0.1 mL, 0.5 mmol). After the
solution was stirred for another 15 min, dimethyl malonate
(0.10 mL, 0.87 mmol), BSA (0.22 mL, 0.87 mmol), and potassiꢀ
um acetate (0.002 g) were added. The reaction mixture was stirred
for 48 h, diluted with hexane (5 mL), and filtered through the
layer of celite. The solvents were evaporated at reduced pressure
(40 Torr), the residue was dried in vacuo (10 Torr). Conversion
of the substrate 4 and enantiomeric excess of the product 7 were
determined by HPLC on a chiral stationary phase.
24. V. Beghetto, A. Scrivanti, U. Matteoli, Catal. Commun.,
2001, 139.
25. H. Park, R. Kumareswaran, T. V. RajanBabu, Tetrahedron,
2005, 61, 6352.
26. K. V. L. Crepy, T. Imamoto, Adv. Synth. Catal., 2003, 345, 79.
27. B. M. Trost, M. L. Crawley, Chem. Rev., 2003, 103, 2921.
28. T. Graening, H.ꢀG. Schmalz, Angew. Chem., Int. Ed., 2003,
42, 2580.
29. Z. Lu, S. Ma, Angew. Chem., Int. Ed., 2008, 47, 258.
30. K. N. Gavrilov, O. G. Bondarev, R. V. Lebedev, A. A.
Shiryaev, S. E. Lyubimov, A. I. Polosukhin, G. V. Grintꢀ
selevꢀKnyazev, K. A. Lyssenko, S. K. Moiseev, N. S. Ikonꢀ
nikov, V. N. Kalinin, V. A. Davankov, A. V. Korostylev,
H.ꢀJ. Gais, Eur. J. Inorg. Chem., 2002, 1367.
This work was financially supported by the Russian
Foundation for Basic Research (Project No. 11ꢀ03ꢀ00347ꢀa)
and the Council on Grants at the President of the Russian
Federation (Program of State Support for Young Rusꢀ
sian ScientistsꢀCandidates of Science (PhD), Grant
MKꢀ3889.2010.3).
31. V. N. Tsarev, S. E. Lyubimov, O. G. Bondarev, A. A. Korlyꢀ
ukov, M. Yu. Antipin, P. V. Petrovskii, V. A. Davankov,
A. A. Shiryaev, E. B. Benetsky, P. A. Vologzhanin, K. N.
Gavrilov, Eur. J. Org. Chem., 2005, 2097.
32. K. N. Gavrilov, M. G. Maksimova, S. V. Zheglov, O. G.
Bondarev, E. B. Benetsky, S. E. Lyubimov, P. V. Petrovskii,
A. A. Kabro, E. HeyꢀHawkins, S. K. Moiseev, V. N. Kalinin,
V. A. Davankov, Eur. J. Org. Chem., 2007, 4940.
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1999, 64, 8940.
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Received February 8, 2011;
in revised form April 5, 2011