First P,P bidentate phosphine-phosphite-type ligand with a Pstereocenter in the phosphite moiety: Synthesis and application in the Pd-catalyzed asymmetric allylic alkylation

Article abstract of DOI:10.1007/s11172-013-0148-4

A new P,P bidentate phosphine-diamidophosphite bearing an asymmetric phosphorus atom in the 1,3,2-diazaphospholidine ring was obtained. A possibility of its application in the palladium-catalyzed enantioselective allylic substitution was demonstrated. A 70% ee was reached in the alkylation of (E)-1,3-diphenylallyl acetate with dimethyl malonate.

Full text of DOI:10.1007/s11172-013-0148-4

Russian Chemical Bulletin, International Edition, Vol. 62, No. 4, pp. 1097—1102, April, 2013
1097
First P,P*ꢀbidentate phosphineꢀphosphiteꢀtype ligand
with a P*ꢀstereocenter in the phosphite moiety: synthesis and application
in the Pdꢀcatalyzed asymmetric allylic alkylation
K. N. Gavrilov,a S. V. Zheglov,a A. A. Shiryaev,a O. V. Potapova,a V. K. Gavrilov,a A. N. Volov,b and I. A. Zamilatskovb
aS. A. Esenin Ryazan State University,
46 ul. Svobody, 390000 Ryazan, Russian Federation.
Fax: +7 (491) 28 1435. Eꢀmail: k.gavrilov@rsu.edu.ru
bA. N. Frumkin Institute of Physical Chemistry and Electrochemistry, Russian Academy of Sciences,
31 Leninsky prosp., 119071 Moscow, Russian Federation.
Fax: +7 (495) 952 0449. Eꢀmail: alex123.87@mail.ru
A new P,P*ꢀbidentate phosphineꢀdiamidophosphite bearing an asymmetric phosphorus
atom in the 1,3,2ꢀdiazaphospholidine ring was obtained. A possibility of its application in the
palladiumꢀcatalyzed enantioselective allylic substitution was demonstrated. A 70% ee was
reached in the alkylation of (E)ꢀ1,3ꢀdiphenylallyl acetate with dimethyl malonate.
Key words: phosphineꢀphosphites, phosphineꢀdiamidophosphites, palladium catalysts,
asymmetric alkylation.
Asymmetric metal complex catalysis is an extremely
powerful means for the preparation of enantiopure or, in
general case, enantioenriched organic and organoelement
compounds. Such compounds are widely used as the main
components of drugs, chemical protection of agricultural
and forest plantations, perfume compositions, food addiꢀ
tives, and fragrances.1—6
limits their wide practical application. In this connection,
a search for the new efficient phosphorusꢀcontaining inꢀ
ductors of chirality easily synthesized from available enanꢀ
tiopure synthons is still an actual problem.11—15
Researchers direct much attention to the hybrid P,Pꢀbiꢀ
dentate phosphineꢀphosphiteꢀtype ligands represented by
phosphineꢀphosphites (C2PC/OPO2) and phosphineꢀ
amidophosphites (C2PC/NPO2).7,16 First, they combine
advantages of both classes of phosphorusꢀcontaining
ligands, for example, a considerable ꢀacidity of the phosꢀ
phite center and unique steric parameters of the phosꢀ
phine center. Second, irrespective of the substrate type of
coordination, such compounds possess the C1ꢀsymmetry,
that favors the asymmetric induction in the key catalytic
intermediate step, as well as they have unsymmetric elecꢀ
tron pattern due to the presence in their structure of phosꢀ
phorus centers with different electron demands. The
ꢀaccepting power of the phosphite center makes it possiꢀ
ble to stabilize the metal complex intermediates in the low
oxidation states of the central complexation ions, while
the ꢀdonating ability of the phosphine center facilitates
the processes of oxidative addition. The different transꢀ
effect of the various phosphorus centers and the essential
asymmetry of the metal center environment also considꢀ
erably contribute to the activity and stereoselectivity of
the metal complex catalysts based on the phosphineꢀphosꢀ
phiteꢀtype ligands.7,14—25
Besides the central complexation atom (ion), coordiꢀ
nated molecules of a substrate, a reagent, and a chiral
ligand are included in the key catalytic intermediate. The
metal center provides a lowꢀenergy pathway for the reacꢀ
tion, while the ligand controls the reactivity and secures
an asymmetric environment. In this way a predominant
discrimination of one of the enantiotopic elements (an
atom, a substituent, or a molecule side) in the structure
of the substrate is achieved.7 Therefore, activity and stereoꢀ
selectivity of the metal complex catalysts are to a great
extent determined by a proper design and synthesis
strategy of the corresponding chiral ligands, first of all,
phosphorusꢀcontaining ligands, thousands representatives
of which were used in various asymmetric transformaꢀ
tions.1,2,4,7—10 Nonetheless, the overwhelming majority of
such ligands in the corresponding metal complexes are
capable of catalyzing only a certain type of chemical transꢀ
formations or even a certain reaction showing a specific
enantioselectivity. There are very few versatile (the soꢀ
called "privileged") ligands, and the high cost significantly
Phosphineꢀphosphite ligands bearing P*ꢀstereocenters
are of special interest. The presence of a stereogenic donor
phosphorus atom significantly promotes the successful
Dedicated to Academician of the Russian Academy of Sciences
I. P. Beletskaya on the occasion of her anniversary.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 1096—1101, April, 2013.
1066ꢀ5285/13/6204ꢀ1097 © 2013 Springer Science+Business Media, Inc.

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Russ.Chem.Bull., Int.Ed., Vol. 62, No. 4, April, 2013
Gavrilov et al.
asymmetric induction in the key step of the catalytic cyꢀ
cle. Since this atom is directly bonded to the central comꢀ
plexation atom (ion), it is positioned very close to the
coordinated substrate, that interferes with a potentially
inefficient secondary transfer of chirality from the ligand
framework.2,15,26 Thus, phosphineꢀphosphites LA—D are
successfully used in the asymmetric reactions of Pdꢀcataꢀ
lyzed allylation, Rhꢀcatalyzed hydroformylation, and Rhꢀ
and Irꢀcatalyzed hydration, while the epimeric phosphineꢀ
amidophosphites LE are used in Agꢀcatalyzed cycloaddiꢀ
tion and Cuꢀcatalyzed conjugate reduction.27—34 All
these ligands have phosphine P*ꢀstereocenters, whereas
P,P*ꢀbidentate stereoselectors of the phosphineꢀphosꢀ
phiteꢀtype with asymmetric phosphorus atoms in the
phosphite moiety are not yet described. There is no litꢀ
erature data on phosphineꢀdiamidophosphites (C2PC/
OPN2), either.
can be easily converted to esters and amides of chiral unꢀ
saturated carboxylic acids.38
Results and Discussion
A oneꢀstep phosphorylation of 2ꢀ(diphenylphosphino)ꢀ
phenylmethanol (1) with (5S)ꢀ2ꢀchloroꢀ3ꢀphenylꢀ1,3ꢀdiꢀ
azaꢀ2ꢀphosphabicyclo[3.3.0]octane (2) in toluene in the
presence of a DMAP catalyst and Et3N as the hydrogen
chloride acceptor yielded P,P*ꢀbidentate phosphineꢀdiꢀ
amidophosphite 3 (Scheme 1).
Scheme 1
In the present work, we report the synthesis of the first
P,P*ꢀbidentate phosphineꢀdiamidophosphite bearing an
asymmetric phosphorus atom in the 1,3,2ꢀdiazaphosꢀ
phaolidine ring and its application in the enantioselective
catalysis. The Pdꢀcatalyzed asymmetric allylic alkylation
was chosen as a test catalytic reaction. On the one
hand, this reaction is a reliable method to evaluate the
efficiency of new chiral ligands. On the other hand,
since this reaction is not very sensitive to different funcꢀ
tional groups in the structure of allylic substrates, it
is actively used in asymmetric synthesis of valuable organꢀ
ic and natural compounds.7,26,35—37 In particular, the
products of alkylation with dimethyl malonate under mild
conditions and without involvement of the C*ꢀstereocenter
Note that the phosphorylating agent 2 was easily obꢀ
tained39 in good yield starting from available (S)ꢀglutamic

The first phosphineꢀphosphiteꢀtype ligand
Russ.Chem.Bull., Int.Ed., Vol. 62, No. 4, April, 2013
1099
acid anilide,40,41 whereas alcohol 1 was obtained by the
reduction of commercial 2ꢀ(diphenylphosphino)benzꢀ
aldehyde with NaBH4 (see Ref. 42). Ligand 3 is a stereoꢀ
individual compound, its 31P NMR spectrum in solution
in CDCl3 exhibits two singlets of equal intensity at P 120.0
and –15.7 related to the diamidophosphite and the phosꢀ
phine phosphorus atoms, respectively. Phosphineꢀdiꢀ
amidophosphite 3 has (R)ꢀconfiguration of the P*ꢀstereoꢀ
center as evidenced by a large spinꢀspin coupling constant
2JC(8),P (37.6 Hz) in the 13C NMR spectrum of its solution
in CDCl3 (see Experimental). Such a value indicates an
antiꢀorientation of the pseudoequatorial exocyclic substitꢀ
uent at the diamidophosphite phosphorus atom and
the fragment —(CH2)3— of the pyrrolidine ring in the
phosphabicyclo[3.3.0]octane skeleton and, therefore,
a synꢀorientation between the lone pair of electrons on the
phosphorus atom and atom C(8) (Fig. 1).39—41,43—45
Compound 3 was easily purified by flashꢀchromatogꢀ
raphy, it is stable enough in air and can be stored for a long
time under dry atmosphere.
Scheme 3
i. CH2(CO2Me)2, Pdꢀcat.
uct 6 predominates, with the enantiomeric purity of 6
varying within 30—70% ee.
When [Pd(allyl)Cl]2 was used as a preꢀcatalyst (see
Table 1, entries 1—14), a higher enantioselectivity was
observed in the reactions in THF and CH2Cl2 compared
to those in toluene and 1,4ꢀdioxane. The influence of bases
(BSA or Cs2CO3) on the stereoinduction varied, however,
with Cs2CO3 almost always considerably higher converꢀ
sion was recorded. Similarly, the influence of the molar
ratio L/Pd on enantioselectivity was not straightforward,
with the highest conversion being observed for L/Pd = 1 in
almost all the cases. The maximal enantioselectivity was
reached in THF in the presence of BSA with the molar
ratio L/Pd = 1 (70% ee, see Table 1, entry 7).
The reaction of ligand 3 with [Pd(allyl)Cl]2 (in the
presence of AgSbF6) leads to the formation of the cationic
metal chelate 4 with cisꢀorientation46,47 of the phosphorus
atoms (Scheme 2).
When the preꢀcatalyst [Pd2(dba)3]•CHCl3 was used,
ligand 3 provided a somewhat lower enantioselectivity (to
60% ee), with CH2Cl2 being the optimal solvent (see
Table 1, entries 15—18). In the catalytic experiment which
used a preꢀsynthesized complex 4 (see Table 1, enꢀ
tries 19—24), the ee reached 56%, with the highest asymꢀ
metric induction being observed for the reaction in CH2Cl2.
The use of Cs2CO3 as the base provided virtually quantitaꢀ
tive conversion (see Table 1, entries 20, 22, and 24).
In conclusion, in the present work we described the
synthesis of the first representative 3 of the phosphineꢀ
phosphiteꢀtype P,P*ꢀbidentate ligands with a stereogenic
phosphorus atom in the phosphite moiety. Its involveꢀ
ment in the model Pdꢀcatalyzed asymmetric allylic alkylaꢀ
tion reaction of (E)ꢀ1,3ꢀdiphenylallyl acetate (5) with diꢀ
methyl malonate provided a good level of enantioselectivꢀ
ity, up to 70% ee. Therefore, phosphineꢀdiamidophosꢀ
phite 3 is a promising stereoselector, whose application
(as well as of other similar P,P*ꢀbidentate ligands with
P*ꢀstereocenters in the 1,3,2ꢀdiazaphosphaolidine rings)
in the practically useful catalytic processes of the C—C
bond formation37,49 is studied in our laboratories.
Scheme 2
In the 31P NMR spectrum of the solution of complex 4
in CDCl3 one can see doublets for two AX systems
2
(P 127.2 and 14.9, JP,P* = 64.0 Hz, 58%; P 127.3 and
13.1, 2JP,P* = 62.3 Hz, 42%) indicating that 4 exists as an
equilibrium mixture of interconversible exoꢀ and endoꢀ
isomers.7,39,46—48
Phosphineꢀdiamidophosphite 3 and its complex 4 were
studied in the Pdꢀcatalyzed asymmetric allylic alkylation
of (E)ꢀ1,3ꢀdiphenylallyl acetate (5) with dimethyl malꢀ
onate (Scheme 3, Table 1).
The data in Table 1 show that the values of conversion
and the asymmetric induction depend on the nature of
preꢀcatalyst, solvent, and base and the molar ratio L/Pd.
In all the cases, the (S)ꢀenantiomer of the reaction prodꢀ
Experimental
31
P, 1H, and 13C NMR spectra were recorded on Bruker
Avance 400 (161.98, 400.13, and 100.61 MHz) and Bruker
Avance III 600 spectrometers (242.94, 600.13, and 150.9 MHz)
relative to 85% H3PO4 in D2O and Me4Si, respectively. The
signals in the 1H and 13C NMR spectra were assigned using
Fig. 1. The structural fragment of ligand 3 (Х is the exocyclic
substituent).

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Russ.Chem.Bull., Int.Ed., Vol. 62, No. 4, April, 2013
Gavrilov et al.
Table 1. Pdꢀcatalyzed alkylation of 5 with dimethyl malonatea
Entry
Palladium
complex
L/Pd
Solvent
Base
Conversion
ee (%)b
1
2
3
4
5
6
7
8
[Pd(allyl)Cl]2
[Pd(allyl)Cl]2
[Pd(allyl)Cl]2
[Pd(allyl)Cl]2
[Pd(allyl)Cl]2
[Pd(allyl)Cl]2
[Pd(allyl)Cl]2
[Pd(allyl)Cl]2
[Pd(allyl)Cl]2
[Pd(allyl)Cl]2
[Pd(allyl)Cl]2
[Pd(allyl)Cl]2
[Pd(allyl)Cl]2
[Pd(allyl)Cl]2
[Pd2(dba)3]•CHCl3
[Pd2(dba)3]•CHCl3
[Pd2(dba)3]•CHCl3
[Pd2(dba)3]•CHCl3
4
1
2
1
2
1
2
1
2
1
2
1
2
1
2
1
2
1
2
1
1
1
1
1
1
Toluene
Toluene
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
THF
THF
THF
THF
1,4ꢀDioxane
1,4ꢀDioxane
1,4ꢀDioxane
1,4ꢀDioxane
CH2Cl2
CH2Cl2
THF
BSA
BSA
BSA
80
21
100
60
100
100
62
10
78
22
60
5
75
9
73
49
0
28
62
100
37
100
98
99
45 (S)
47 (S)
47 (S)
54 (S)
57 (S)
53 (S)
70 (S)
47 (S)
36 (S)
46 (S)
40 (S)
50 (S)
44 (S)
44 (S)
51 (S)
60 (S)
—
53 (S)
56 (S)
54 (S)
30 (S)
52 (S)
46 (S)
40 (S)
BSA
Cs2CO3
Cs2CO3
BSA
BSA
9
Cs2CO3
Cs2CO3
BSA
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
BSA
Cs2CO3
Cs2CO3
BSA
BSA
BSA
BSA
BSA
Cs2CO3
BSA
Cs2CO3
BSA
THF
CH2Cl2
CH2Cl2
THF
THF
1,4ꢀDioxane
1,4ꢀDioxane
4
4
4
4
4
Cs2CO3
a All the reactions were carried out at 20 C, for 48 h, with 2 mol.% [Pd(allyl)Cl]2 or [Pd2(dba)3]•CHCl3.
b Conversion of substrate 5 and enantiomeric excess of product 6 were determined by HPLC (Daicel
Chiralcel OD—H, C6H14/PriOH = 99 : 1, 0.6 mL min–1, 254 nm).
COSY, DEPT, and HSQC procedures, as well as taking into
account the data in the works.30,31,39—41 Mass spectra of laser
desorption ionization (MALDI TOF/TOF) were recorded on
a Bruker Daltonics Ultraflex instrument. Enantiomeric compoꢀ
sition of the catalytic reaction products was analyzed on a Staier
HPLꢀchromatograph. Elemental analysis was performed in the
Laboratory of organic microanalysis of the A. N. Nesmeyanov
Institute of Organoelement Compounds of the Russian Acadeꢀ
my of Sciences.
All the reactions were carried out under dry argon in anhyꢀ
drous solvents. The starting substrate (E)ꢀ1,3ꢀdiphenylallyl aceꢀ
tate (5), as well as complexes [Pd(allyl)Cl]2 and [Pd2(dba)3]•
•CHCl3 were obtained according to the known procedures.50,51
Catalytic experiments of the asymmetric alkylation of substrate 5
with dimethyl malonate, determination of conversion of 5 and
enantiomeric excesses of product 6 were carried out following by
the procedure published earlier.39
2ꢀ(Diphenylphosphino)benzaldehyde, dimethyl malonate,
bisꢀtrimethylsilylacetamide (BSA), 4ꢀdimethylaminopyridine
(DMAP), and AgSbF6 were commercially available from Fluka
and Aldrich.
(2R,5S)ꢀ2ꢀ[2ꢀ(Diphenylphosphino)phenylmethoxy]ꢀ3ꢀpheꢀ
nylꢀ1,3ꢀdiazaꢀ2ꢀphosphabicyclo[3.3.0]octane (3). A solution of
2ꢀ(diphenylphosphino)phenylmethanol 2 (0.59 g, 2 mmol) in
toluene (5 mL) was added was added dropwise during 20 min at
20 C to a vigorously stirred solution of phosphorylating agent 1
(0.48 g, 2 mmol), Et3N (0.5 mL, 3.6 mmol), and catalyst DMAP
(0.024 g, 0.2 mmol) in toluene (10 mL). The mixture obtained
was refluxed for 15 min and cooled to 20 C, a precipitate of
Et3N•HCl was filtered off. The filtrate was concentrated in vacꢀ
uo (40 Torr). The product obtained was purified by flashꢀchroꢀ
matography on alumina, eluent toluene. The yield was 0.83 g
(84%), colorless dense oil. Found (%): C, 72.85; H, 6.16; N, 5.44.
C30H30N2OP2. Calculated (%): C, 72.57; H, 6.09; N, 5.64.
3
13C NMR (CDCl3), : 26.3 (d, C(7), JC,P = 4.1 Hz); 32.1
(s, C(6)); 48.4 (d, C(8), 2JC,P = 37.6 Hz); 54.9 (d, C(4), 2JC,P
=
2
3
= 7.6 Hz); 61.8 (dd, CH2O, JC,P = 27.5 Hz, JC,P = 4.8 Hz);
63.2 (d, C(5), 2JC,P = 8.8 Hz); 114.9 (d, CHPhN, 3JC,P = 12.2 Hz);
118.8 (s, CHPhN); 127.0 (d, CHPhP,
3JC,P = 5.3 Hz); 127.1
(s, CHPhP); 128.6 (d, CHPhP, 3JC,P = 6.9 Hz); 128.7 (s, CHPhP);
128.8 (s, CHPhP); 128.9 (s, CHPhP); 129.0 (s, CHPhN); 132.6 (s,
CHPhP); 133.8 (s, CHPhP); 134.0 (s, CHPhP); 134.2 (s, CHPhP);
136.1 (d, CPhP, 1JC,P = 9.8 Hz); 136.2 (d, CPhP, 1JC,P = 10.1 Hz);
3
143.0 (dd, CPhP
(d, CPhN
,
2JC,P = 21.7 Hz, JC,P = 2.6 Hz); 145.7
,
2JC,P = 16.3 Hz). 1H NMR (CDCl3), : 1.54—1.60
(m, 1 H, C(6)H); 1.71—1.82 (m, 2 H, C(7)H2); 1.94—2.0
(m, 1 H, C(6)H); 3.05—3.14 (m, 2 H, C(8)H and C(4)H);
3.50—3.57 (m, 2 H, C(8)H and C(4)H); 3.88—3.92 (m, 1 H,
C(5)H); 4.72 (dd, 1 H, CHO, 2JH,H = 13.4 Hz, 3JH,P = 5.4 Hz);
4.99 (ddd, 1 H, CHO, 2JH,H = 13.4 Hz, 3JH,P = 6.0 Hz, 4JH,P
=
= 2.1 Hz); 6.82 (t, 1 H, CHPhP,
3J = 6.4 Hz); 6.85 (t, 1 H,
CHPhN
,
3J = 7.2 Hz); 7.0 (d, 2 H, CHPhN
,
3J = 8.4 Hz); 7.15
3
(t, 1 H, CHPhP, J = 7.2 Hz); 7.21—7.26 (m, 2 H, CHPhN and
1 H, CHPhP); 7.28—7.39 (m, 10 H, CHPhP); 7.6—7.62 (m, 1 H,

The first phosphineꢀphosphiteꢀtype ligand
Russ.Chem.Bull., Int.Ed., Vol. 62, No. 4, April, 2013
1101
CHPhP). MS (MALDI TOF/TOF), m/z (Irel (%)): 535 [M + K]+
(100), 497 [M + H]+ (17).
7. H. FernandezꢀPerez, P. Etayo, A. Panossian, A. VidalꢀFerꢀ
ran, Chem. Rev., 2011, 111, 2119.
{(2R,5S)ꢀ2ꢀ[2ꢀ(Diphenylphosphino)phenylmethoxy]ꢀ3ꢀpheꢀ
nylꢀ1,3ꢀdiazaꢀ2ꢀphosphabicyclo[3.3.0]octaneꢀP,P*}(ꢀallyl)ꢀ
palladium(2+) hexafluoroantimonate (4). A solution of P,P*ꢀbiꢀ
dentate ligand 3 (0.1 g, 0.2 mmol) in CH2Cl2 (2 mL) was added
dropwise during 30 min to a stirred solution of [Pd(All)Cl]2 (0.037 g,
0.1 mmol) in CH2Cl2 (1 mL) at 20 C. The reaction mixture was
stirred for another 1 h at 20 C. Then, a solution of AgSbF6
(0.069 g, 0.2 mmol) in CH2Cl2 (2 mL) was added dropwise during
30 min to the solution obtained and the reaction mixture was
stirred for 1.5 h at 20 C. A precipitate of AgCl was filtered off.
Excessive solvent was evaporated at reduced pressure (40 Torr)
to the volume of ~0.5 mL) and diethyl ether (7 mL) was added.
A precipitate formed was separated by centrifugation, washed
with diethyl ether (2×5 mL) and hexane (2×5 mL), dried in air
and in vacuo (1 Torr). The yield was 0.162 g (92%), a powder
light yellow, m.p. 180—183 C (with decomp.). Found (%):
C, 45.31; H, 3.82; N, 3.24. C33H35F6N2OP2PdSb. Calculated (%):
C, 45.05; H, 4.01; N, 3.18. MS (MALDI TOF/TOF), m/z
(Irel (%)): 643 [M – SbF6]+ (44), 602 [M – All – SbF6]+ (100).
Asymmetric alkylation of (E)ꢀ1,3ꢀdiphenylallyl acetate (5) with
dimethyl malonate. A solution of [Pd(allyl)Cl]2 (0.0037 g,
0.01 mmol) or [Pd2(dba)3]•CHCl3 (0.01 g, 0.01 mmol) and the
corresponding ligand (0.01 g, 0.02 mmol or 0.02 g, 0.04 mmol)
in the corresponding solvent (5 mL) were stirred for 40 min or
complex 4 (0.0176 g, 0.02 mmol) was dissolved in the correꢀ
sponding (5 mL) solvent, followed by the addition of (E)ꢀ1,3ꢀ
diphenylallyl acetate (0.1 mL, 0.5 mmol), and the solution was
stirred for another 15 min. Then, dimethyl malonate (0.1 mL,
0.87 mmol), BSA (0.22 mL, 0.87 mmol), and potassium acetate
(0.002 g) or dimethyl malonate (0.1 mL, 0.87 mmol) and cesium
carbonate (0.163 g, 0.5 mmol) were added. The reaction mixture
was stirred for 48 h, diluted with hexane (5 mL) and filtered
through Celite. The solvents were evaporated at reduced presꢀ
sure (40 Torr), the residue was dried in vacuo (10 Torr). Converꢀ
sion of substrate 5 and enantiomeric excess of products 6 were
determined by HPLC on a chiral stationary phase.
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Received December 21, 2012;
in revised form February 8, 2013