Palladium-catalyzed allylic substitution assisted by 1,3,2- diazaphospholidine derivatives of (R,R)-N-naphthyltartarimide

Article abstract of DOI:10.1007/s11172-010-0228-7

P,P-Bidentate diamidophosphite ligands containing the (3R,4R)-3,4-dioxy-1- (1-naphthyl)pyrrolidine-2,5-dione framework and 1,3,2-diazaphospholidine rings with the stereogenic P atoms were obtained. The use of these ligands provides up to 85% ee in Pd-cata

Full text of DOI:10.1007/s11172-010-0228-7

Russian Chemical Bulletin, International Edition, Vol. 59, No. 6, pp. 1242—1247, June, 2010
1242
Palladiumꢀcatalyzed allylic substitution assisted
by 1,3,2ꢀdiazaphospholidine derivatives of (R,R)ꢀNꢀnaphthyltartarimide
K. N. Gavrilov,a E. A. Rastorguev,b S. V. Zheglov,a N. N. Groshkin,a V. E. Boyko,a A. S. Safronov,b
P. V. Petrovskii,b and V. A. Davankovb
aS. A. Esenin Ryazan State University,
46 ul. Svobody, 390000 Ryazan, Russian Federation.
Fax: +7 (491 2) 77 5498. 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
P,PꢀBidentate diamidophosphite ligands containing the (3R,4R)ꢀ3,4ꢀdioxyꢀ1ꢀ
(1ꢀnaphthyl)pyrrolidineꢀ2,5ꢀdione framework and 1,3,2ꢀdiazaphospholidine rings with the steꢀ
reogenic P atoms were obtained. The use of these ligands provides up to 85% ee in Pdꢀcatalyzed
asymmetric amination of (E)ꢀ1,3ꢀdiphenylallyl acetate and up to 95% ee in its asymmetric
alkylation with dimethyl malonate.
Key words: ligands, diamidophosphites, 1,3,2ꢀdiazaphospholidines, palladium catalysts,
asymmetric amination, asymmetric alkylation.
The preparation of drugs, chemical agents for plant
N atoms, one can control its steric and electronic parameꢀ
ters.29,30 If the electronꢀdonating P atom is asymmetric,
this substantially promotes chirality transfer in the key
step of the catalytic cycle.2
In the present work, we report on the synthesis of
P,Pꢀbidentate diamidophosphites 1 and 2 and their use
for enantioselective catalysis (Scheme 1). The 1,3,2ꢀdiꢀ
azaphospholidine rings in these ligands are linked to the
sterically rigid tartarimide (3,4ꢀdioxypyrrolidineꢀ2,5ꢀ
dione) ring. Note that known ligands with the pyrrolidineꢀ
2,5ꢀdione fragment LA—C are efficient stereoselectors in
Pdꢀcatalyzed allylic substitution and Rhꢀcatalyzed hydroꢀ
genation.31—33
We tested compounds 1 and 2 in Pdꢀcatalyzed asymꢀ
metric allylation, which is an effective tool for (1) estimaꢀ
tion of the efficiency of novel chiral ligands and (2) stereoꢀ
selective synthesis of valuable natural compounds.14,34—37
We also compared the asymmetryꢀinducing activity of
both ligands 1 and 2 themselves and their known analogs
LB and LC.
protection, food additives, flavors, and stereoindividual
polymers is based on modern approaches to the synthesis
of optically pure compounds. One of the leading approachꢀ
es is asymmetric metal complex catalysis.1—5 In turn, the
activity and stereoselectivity of metal complex catalysts
largely depend on the successful strategy of design and
synthesis of appropriate chiral ligands, among which phosꢀ
phorusꢀcontaining compounds are worth noting.6,7 Along
with classic P,Pꢀbidentate phosphines, P,Pꢀbidentate
phosphite ligands are successfully used because they can
simply be prepared from accessible precursors, are inert to
oxidants, exhibit pronounced πꢀacidity, and are less exꢀ
pensive.8—14 The main attention of researchers is focused
on P,Pꢀbidentate phosphites containing 1,3,2ꢀdioxaphosꢀ
phepine rings based on BINOL, H8ꢀBINOL, and various
2,2´ꢀdihydroxyꢀ1,1´ꢀbiphenyls.13—22
Our investigations deal with the synthesis of various
diamidophosphites containing stereogenic P atoms and
1,3,2ꢀdiazaphospholidine rings and their use in asymmetric
catalytic reactions.23—28 It should be noted that 1,3,2ꢀdiꢀ
azaphospholidines, including P*ꢀchiral ones, are an atꢀ
tractive group of optically active diamidophosphite ligands.
For instance, they have balanced electron characteristics:
they are both good πꢀacceptors (because of the accessibilꢀ
ity of the lowꢀenergy π*PNꢀorbitals) and good σꢀdonors.
Inclusion of a phosphorus atom into the fiveꢀmembered
ring makes the ligand more resistant to oxidation and
hydrolysis; by widely varying the substituents at the
Results and Discussion
Novel P,Pꢀbidentate diamidophosphites 1 and 2 were
obtained by direct phosphorylation of (R,R)ꢀNꢀnaphthylꢀ
tartarimide 3 with reagents 4 and 5 in THF (see Scheme 1).
Note that the starting chiral diol 3 is easily accessible
through highꢀyielding condensation of (R,R)ꢀtartaric acid
with 1ꢀnaphthylamine.38 Ligand 1 is stereochemically inꢀ
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1216—1222, June, 2010.
1066ꢀ5285/10/5906ꢀ1242 © 2010 Springer Science+Business Media, Inc.

Asymmetric allylation
Russ.Chem.Bull., Int.Ed., Vol. 59, No. 6, June, 2010
1243
dividual; its P*ꢀstereocenters have (R)ꢀconfiguration,
which is evident from the presence of narrow singlets at δP
130.5 and 130.3 in the 31P NMR spectrum of its solution
ly, the cisꢀorientation of the lone electron pair of the
P atom and the C(8´) atom (Fig. 1).23,33,39—44
The 31P NMR spectrum of ligand 2 in CDCl3 also
exhibits two narrow singlets of equal intensities at δP 112.4
and 112.1. The presence of two signals in the 31P NMR
spectra of diamidophosphites 1 and 2 is due to the nonꢀ
equivalence of their phosphorus centers. Such a nonequivꢀ
alence is confirmed by different Tolman conical angles θ
of the phosphorus centers: according to semiempirical
in CDCl3 and from the high coupling constant 2JC(8´),P
=
= 35.5 Hz in the 13C NMR spectrum (see Experimental).
This value suggests the antiꢀorientation of the pseudoequaꢀ
torial exocyclic substituent at the P atom and the fragꢀ
ment —(CH2)3— of the pyrrolidine ring of the diazaꢀ
phosphabicyclo[3.3.0]octane framework and, consequentꢀ
Scheme 1
2 Et3N, THF
2 Et3N, THF

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Russ.Chem.Bull., Int.Ed., Vol. 59, No. 6, June, 2010
Gavrilov et al.
Table 1. Data for the Pdꢀcatalyzed allylic amination of comꢀ
pound 6 with pyrrolidinea
Entry
Catalyst
Solvent Conversion
(%)
ee
(%)b
1
2
3
4
5
6
7
8
[Pd(allyl)Cl]2—2[1]
[Pd(allyl)Cl]2—4[1]
[Pd(allyl)Cl]2—2[1]
[Pd(allyl)Cl]2—4[1]
[Pd(allyl)Cl]2—2[2]
[Pd(allyl)Cl]2—4[2]
[Pd(allyl)Cl]2—2[2]
[Pd(allyl)Cl]2—4[2]
THF
THF
CH2Cl2
CH2Cl2
THF
THF
CH2Cl2
CH2Cl2
87
59
67
100
100
100
100
100
73 (R)
30 (R)
65 (R)
45 (R)
11 (S)
9 (S)
Fig. 1. Fragment of structure 1 (X is an exocyclic substituent).
AM1 calculations with full optimization of the geometriꢀ
cal parameters, θ = 159° and 147° in ligand 1 and θ = 205°
and 186° in ligand 2.45,46
Compounds 1 and 2 can easily be purified by flash
chromatography, are fairly stable in air, and can be stored
in a dry atmosphere for a long period of time. Since the
starting synthons are accessible, ligands 1 and 2 can be
prepared in amounts of multigrams.
Diamidophosphites 1 and 2 were tested in Pdꢀcataꢀ
lyzed asymmetric amination and alkylation of (E)ꢀ1,3ꢀdiꢀ
phenylallyl acetate (6) using [Pd(allyl)Cl]2 as a palladium
source (Scheme 2, Tables 1—3).
20 (S)
7 (S)
a All reactions were carried out at 20 °C for 48 h in the presence
of [Pd(allyl)Cl]2 (2 mol.%).
b The conversion of substrate 6 and the enantiomer excesses of
product 7 were determined by HPLC (Daicel Chiralcel OD—H,
C6H14/PriOH/HNEt2 = 200 : 1 : 0.1, 0.9 mL min–1, 254 nm).
dine, the better asymmetric induction is achieved in THF
but for L/Pd = 2. The conversions of substrate 6 are comꢀ
parable in both solvents.
Scheme 2
Allylic alkylation of compound 6 with dimethyl malꢀ
onate in the presence of P*,P*ꢀbidentate ligand 1 gives
product (S)ꢀ9 with 91—95% ee (Scheme 2, Table 3,
entries 3, 4); the starting substrate is fully converted,
regardless of the molar ratio L/Pd. In contrast to the allylꢀ
ic amination, the optimum solvent for this reaction is
CH2Cl2 (see Table 3, cf. entries 1, 2 and 3, 4). Palladium
complexes with ligand 2 favor the formation of product
(R)ꢀ9; the highest enantioselectivity is 31% ee (see Table 3,
entries 5—8).
Compounds 1 and 2 were also used in Pdꢀcatalyzed
asymmetric alkylation of a cyclic substrate, namely, cycloꢀ
hexꢀ2ꢀenꢀ1ꢀyl ethyl carbonate (10), with dimethyl malꢀ
onate (Scheme 3, Table 4). Diamidophosphite 1 provides
up to 46% ee and the 90% conversion of substrate 10
(CH2Cl2, L/Pd = 1; see Table 4, entry 3).
BSA is N,Oꢀbis(trimethylsilyl)acetamide
Table 2. Data for the Pdꢀcatalyzed allylic amination of comꢀ
pound 6 with dipropylaminea
Allylic amination of compound 6 with pyrrolidine in
the presence of ligand 1 gives product (R)ꢀ7 with up to
73% ee. The reaction in THF is more enantioselective,
while the higher conversion was achieved in CH2Cl2 (see
Table 1, entries 1—4), with the optimum molar ratio
L/Pd = 1. An increase in this ratio to two lowers the
asymmetric induction in both THF and CH2Cl2. Ligand 2
provides the 100% conversion of substrate 6, although this
reaction is less enantioselective (at most 20% ee) and
the resulting amine 7 has (S)ꢀconfiguration (Table 1, enꢀ
tries 5—8).
Entry
Catalyst
Solvent Conversion
(%)
ee
(%)b
1
2
3
4
[Pd(allyl)Cl]2—2[1]
[Pd(allyl)Cl]2—4[1]
[Pd(allyl)Cl]2—2[1]
[Pd(allyl)Cl]2—4[1]
THF
THF
CH2Cl2
CH2Cl2
90
78
98
64
49 (+)
85 (+)
47 (+)
41 (+)
a All reactions were carried out at 20 °C for 48 h in the presence
of [Pd(allyl)Cl]2 (2 mol.%).
b The conversion of substrate 6 and the enantiomer excesses of
product 8 were determined by HPLC (Daicel Chiralcel OD—H,
C6H14/PriOH/HNEt2 = 1000 : 1 : 1, 0.4 mL min–1, 254 nm,
t(+) = 8.2 min, t(–) = 9.1 min).
With diamidophosphite 1 as a ligand and with diproꢀ
pylamine as a Nꢀnucleophile, the highest enantioselectivꢀ
ity is 85% ee (Table 2). As in the amination with pyrroliꢀ

Asymmetric allylation
Russ.Chem.Bull., Int.Ed., Vol. 59, No. 6, June, 2010
1245
Table 3. Data for the Pdꢀcatalyzed allylic alkylation of comꢀ
pound 6 with dimethyl malonatea
and 2 favor the formation of the opposite enantiomers of
product 11.
To sum up, one can conclude that diamidophosphite 1
containing the asymmetric P atoms is an efficient stereoꢀ
selector and successfully supplements similar diastereoꢀ
meric ligands LC (see Ref. 33). In particular, being not less
enantioselective than LC in the Pdꢀcatalyzed amination of
(E)ꢀ1,3ꢀdiphenylallyl acetate (6) with pyrrolidine (73 and
73% ee) and in its Pdꢀcatalyzed alkylation with dimethyl
malonate (96 and 95% ee), ligand 1 is superior to them in
the amination of compound 6 with dipropylamine (73 and
85% ee) but somewhat inferior in the Pdꢀcatalyzed alkylaꢀ
tion of cyclohexꢀ2ꢀenꢀ1ꢀyl ethyl carbonate (10) with diꢀ
methyl malonate (65 and 46% ee). In the Pdꢀcatalyzed
alkylation of (E)ꢀ1,3ꢀdiphenylallyl acetate with dimethyl
malonate, ligand 1 is slightly superior to P,Pꢀbidentate
phosphite LB in asymmetric induction (see Ref. 32) (95 and
90% ee, respectively). At the same time, diamidophosꢀ
phite 2 with the C*ꢀstereocenters only in the pyrrolidineꢀ
2,5ꢀdione ring is an inefficient stereoselector, although its
steric demands are higher than those of ligand 1 (for the
Tolman conical angles of the phosphorus centers in 1 and
2, see above). Thus, the pyrrolidineꢀ2,5ꢀdione fragment in
efficient ligands 1 and LA—C forms a sterically rigid basis
and additional P*ꢀ and/or C*ꢀstereocenters should be
present in their structures for achieving high catalytic enanꢀ
tioselectivity.
Entry
Catalyst
Solvent Conversion
(%)
ee
(%)b
1
2
3
4
5
6
7
8
[Pd(allyl)Cl]2—2[1]
[Pd(allyl)Cl]2—4[1]
[Pd(allyl)Cl]2—2[1]
[Pd(allyl)Cl]2—4[1]
[Pd(allyl)Cl]2—2[2]
[Pd(allyl)Cl]2—4[2]
[Pd(allyl)Cl]2—2[2]
[Pd(allyl)Cl]2—4[2]
THF
THF
58
42
33 (S)
70 (S)
91 (S)
95 (S)
31 (R)
11 (R)
20 (R)
5 (R)
CH2Cl2
CH2Cl2
THF
100
100
62
THF
91
CH2Cl2
CH2Cl2
95
100
a All reactions were carried out at 20 °C for 48 h in the presence
of [Pd(allyl)Cl]2 (2 mol.%).
b The conversion of substrate 6 and the enantiomer excesses of
product 9 were determined by HPLC (Daicel Chiralcel OD—H,
C6H14/PriOH = 99 : 1, 0.6 mL min–1, 254 nm).
Scheme 3
Experimental
This result is acceptable since a high enantioselectivity
is difficult to achieve for cyclic substrate 10.14,37,47 The
asymmetric induction in the presence of ligand 2 is low
(7—11% ee; see Table 4, entries 5—8). Interestingly,
in this reaction, as in the above allylic substitution
of (E)ꢀ1,3ꢀdiphenylallyl acetate, diamidophosphites 1
31
P, 1H, and 13C NMR spectra were recorded on a Bruker
AMXꢀ400 instrument (161.98, 400.13, and 100.61 MHz, respecꢀ
tively) with reference to 85% H3PO4 in D2O (31P) and Me4Si
(1H, 13C). The signals in the 13C NMR spectra were assigned
using the DEPT procedure. Mass spectra (MALDI TOF/TOF)
were measured on a Bruker Daltonics Ultraflex instrument.
IR spectra were recorded on a Specord Mꢀ80 instrument (CHCl3,
polyethylene cell). Enantiomer analysis of the products was perꢀ
formed on an HP Agilent 1100 chromatograph. Elemental analꢀ
ysis was carried out at the Organic Microanalysis Laboratory of
the A. N. Nesmeyanov Institute of Organoelement Compounds,
Russian Academy of Sciences.
All reactions were carried out under dry argon in dry solꢀ
vents. The starting complex [Pd(allyl)Cl]2, (3R,4R)ꢀ3,4ꢀdiꢀ
hydroxyꢀ1ꢀ(1ꢀnaphthyl)pyrrolidineꢀ2,5ꢀdione (3), and the phosꢀ
phorylating reagents (5S)ꢀ2ꢀchloroꢀ3ꢀphenylꢀ1,3ꢀdiazaꢀ2ꢀphosꢀ
phabicyclo[3.3.0]octane (4) and 2ꢀchloroꢀ1,3ꢀdiphenylꢀ1,3,2ꢀ
diazaphospholidine (5) were prepared according to known proꢀ
cedures.23,38,48,49
The starting substrates (E)ꢀ1,3ꢀdiphenylallyl acetate (6) and
cyclohexꢀ2ꢀenꢀ1ꢀyl ethyl carbonate (10) were prepared as deꢀ
scribed earlier.49,50 Palladiumꢀcatalyzed asymmetric amination
of substrate 6 with pyrrolidine and dipropylamine and alkylation
of substrate 6 with dimethyl malonate, as well as determination
of its conversion and the enantiomer excesses of products 7—9,
were carried out according to published procedures.51,52,23 Catꢀ
alytic asymmetric alkylation of substrate 10 with dimethyl malꢀ
Table 4. Data for the Pdꢀcatalyzed allylic alkylation of comꢀ
pound 10 with dimethyl malonatea
Entry
Catalyst
Solvent Conversion
(%)
ee
(%)b
1
2
3
4
5
6
7
8
[Pd(allyl)Cl]2—2[1]
[Pd(allyl)Cl]2—4[1]
[Pd(allyl)Cl]2—2[1]
[Pd(allyl)Cl]2—4[1]
[Pd(allyl)Cl]2—2[2]
[Pd(allyl)Cl]2—4[2]
[Pd(allyl)Cl]2—2[2]
[Pd(allyl)Cl]2—4[2]
THF
THF
CH2Cl2
CH2Cl2
THF
THF
CH2Cl2
CH2Cl2
56
59
90
74
39
54
25
54
33 (R)
25 (R)
46 (R)
15 (R)
7 (S)
11 (S)
9 (S)
10 (S)
a All reactions were carried out at 20 °C for 48 h in the presence
of [Pd(allyl)Cl]2 (2 mol.%).
b The conversion of substrate 10 and the enantiomer excesses of
product 11 were determined by HPLC (Daicel Chiralcel AD,
C6H14/PriOH = 200 : 1, 1 mL min–1, 219 nm).

1246
Russ.Chem.Bull., Int.Ed., Vol. 59, No. 6, June, 2010
Gavrilov et al.
onate and determination of its conversion and the enantiomer
excesses of product 11 were carried out as described earlier.53,54
(R,R)ꢀTartaric acid, 1ꢀnaphthylamine, pyrrolidine, diproꢀ
pylamine, dimethyl malonate, and N,Oꢀbis(trimethylsilyl)ꢀ
acetamide (BSA) were the Fluka and Aldrich chemicals.
Synthesis of P,Pꢀbidentate ligands 1 and 2 (general proceꢀ
dure). A solution of (3R,4R)ꢀ3,4ꢀdihydroxyꢀ1ꢀ(1ꢀnaphthyl)ꢀ
pyrrolidineꢀ2,5ꢀdione (3) (1.29 g, 5 mmol) in THF (15 mL) was
added dropwise at 20 °C for 20 min to a vigorously stirred soluꢀ
tion of (5S)ꢀ2ꢀchloroꢀ3ꢀphenylꢀ1,3ꢀdiazaꢀ2ꢀphosphabicycloꢀ
[3.3.0]octane (4) (2.41 g, 10 mmol) or 2ꢀchloroꢀ1,3ꢀdiphenylꢀ
1,3,2ꢀdiazaphospholidine (5) (2.77 g, 10 mmol) and Et3N
(1.45 mL, 10.4 mmol) in THF (25 mL). The reaction mixture
was refluxed with stirring for 1.5 h and cooled to 20 °C. The salt
Et3N•HCl was filtered off and the filtrate was concentrated
in vacuo (40 Torr). Products 1 and 2 were purified by flash chroꢀ
matography on silica gel with hexane—ethyl acetate (1 : 1) (1)
and hexane—CH2Cl2 (1 : 1) (2) as eluents.
(3R,4R)ꢀ1ꢀ(1ꢀNaphthyl)ꢀ3,4ꢀbis[(2R,5S)ꢀ3ꢀphenylꢀ1,3ꢀdiꢀ
azaꢀ2ꢀphosphabicyclo[3.3.0]octꢀ2ꢀyloxy]pyrrolidineꢀ2,5ꢀdione
(1). Yield 2.73 g (82%), yellow powder. Found (%): C, 65.14;
H, 5.66; N, 10.31. C36H37N5O4P2. Calculated (%): C, 64.96;
H, 5.60; N, 10.52. 13C NMR (CDCl3), δ: 26.4 (d, C(7´), 3J =
= 4.4 Hz); 32.0 (s, C(6´)); 48.1 (d, C(8´), 2J = 35.5 Hz); 53.7
(d, C(4´), 2J = 7.8 Hz); 62.7 (d, C(5´), 2J = 8.1 Hz); 74.9
(s, CHO); 75.7 (s, CHO); 115.3 (d, CHPh, 3J = 13.0 Hz); 119.7
(s, CHPh); 121.6 (s, CHNaphthyl); 124.8 (s, CHNaphthyl); 125.9
(s, CHNaphthyl); 126.8 (s, CNaphthyl); 127.0 (s, CHNaphthyl); 127.9
(s, CHNaphthyl); 128.1 (s, CHNaphthyl); 128.9 (s, CHPh); 129.8
(s, CHNaphthyl); 131.4 (s, CNaphthyl); 136.4 (s, CNaphthyl); 145.1
(d, CPh, 2J = 16.1 Hz); 174.6 (s, C=O); 175.1 (s, C=O). 1H NMR
(CDCl3), δ: 1.47 (dq, 2 H, J = 10.8 Hz); 1.7 (m, 4 H); 1.88 (dq, 2 H,
J = 10.9 Hz); 2.93 (ddd, 2 H, J = 8.0 Hz, J = 7.1 Hz, J = 5.9 Hz);
3.22 (m, 2 H); 3.64 (m, 4 H); 3.89 (m, 2 H); 4.77 (s, 1 H); 4.84
(s, 1 H); 6.83 (t, 2 H, J = 7.8 Hz); 7.08 (d, 4 H, J = 8.0 Hz); 7.16
(m, 5 H); 7.33 (m, 2 H); 7.50 (m, 2 H); 7.82 (t, 1 H, J = 8.3 Hz);
7.91 (m, 1 H). IR (CHCl3), ν/cm–1: 1737 (C=O). MS (MALDI
TOF/TOF), m/z (Irel (%)): 689 (100) [M + Na]+, 667 (89)
[M + H]+.
ing solution was stirred for 15 min, whereupon freshly distilled
pyrrolidine (0.12 mL, 1.5 mmol) was added. The reaction mixꢀ
ture was stirred for 48 h, diluted with hexane (5 mL), and filtered
through Celite. The solvents were removed under reduced presꢀ
sure (40 Torr) and the residue was dried in vacuo (10 Torr). The
conversion of substrate 6 and the enantiomer excesses of product
7 were determined by HPLC on a chiral stationary phase.
Asymmetric allylic amination of (E)ꢀ1,3ꢀdiphenylallyl acetate
(6) with dipropylamine. A solution of [Pd(allyl)Cl]2 (0.0037 g,
0.01 mmol) and an appropriate ligand (0.02 or 0.04 mmol) in an
appropriate solvent (5 mL) was stirred for 40 min. Then (E)ꢀ1,3ꢀ
diphenylallyl acetate (0.1 mL, 0.5 mmol) was added. The resultꢀ
ing solution was stirred for 15 min, whereupon freshly distilled
dipropylamine (0.15 mL, 1.5 mmol) was added. The reaction
mixture was stirred for 48 h, diluted with hexane (5 mL), and
filtered through Celite. The solvents were removed under reꢀ
duced pressure (40 Torr) and the residue was dried in vacuo
(10 Torr). The conversion of substrate 6 and the enantiomer
excesses of product 8 were determined by HPLC on a chiral
stationary phase.
Asymmetric allylic alkylation of (E)ꢀ1,3ꢀdiphenylallyl acetate
(6) with dimethyl malonate. A solution of [Pd(allyl)Cl]2 (0.0037 g,
0.01 mmol) and an appropriate ligand (0.02 or 0.04 mmol) in an
appropriate solvent (5 mL) was stirred for 40 min. Then (E)ꢀ1,3ꢀ
diphenylallyl acetate (0.1 mL, 0.5 mmol) was added. The resultꢀ
ing solution was stirred for 15 min, whereupon dimethyl malꢀ
onate (0.10 mL, 0.87 mmol), BSA (0.22 mL, 0.87 mmol), and
potassium acetate (0.002 g) were added. The reaction mixture
was stirred for 48 h, diluted with hexane (5 mL), and filtered
through Celite. The solvents were removed under reduced presꢀ
sure (40 Torr) and the residue was dried in vacuo (10 Torr). The
conversion of substrate 6 and the enantiomer excesses of product 9
were determined by HPLC on a chiral stationary phase.
Asymmetric allylic alkylation of cyclohexꢀ2ꢀenꢀ1ꢀyl ethyl carꢀ
bonate (10) with dimethyl malonate. A solution of [Pd(allyl)Cl]2
(0.0037 g, 0.01 mmol) and an appropriate ligand (0.02 or
0.04 mmol) in an appropriate solvent (5 mL) was stirred for
40 min. Then cyclohexꢀ2ꢀenꢀ1ꢀyl ethyl carbonate (0.085 g,
0.5 mmol) was added. The resulting solution was stirred for
15 min, whereupon dimethyl malonate (0.10 mL, 0.87 mmol),
N,Oꢀbis(trimethylsilyl)acetamide (0.22 mL, 0.87 mmol), and
potassium acetate (0.002 g) were added. The reaction mixꢀ
ture was stirred for 48 h, diluted with hexane (5 mL), and filꢀ
tered through Celite. The solvents were removed under reduced
pressure (40 Torr) and the residue was dried in vacuo (10 Torr).
The conversion of substrate 10 and the enantiomer excesses
of product 11 were determined by HPLC on a chiral stationꢀ
ary phase.
(3R,4R)ꢀ3,4ꢀBis(1,3ꢀdiphenylꢀ1,3,2ꢀdiazaphospholidinꢀ2ꢀ
yloxy)ꢀ1ꢀ(1ꢀnaphthyl)pyrrolidineꢀ2,5ꢀdione (2). Yield 2.88 g
(78%), white powder. Found (%): C, 68.62; H, 5.19; N, 9.58.
C42H37N5O4P2. Calculated (%): C, 68.38; H, 5.06; N, 9.49.
13C NMR (CDCl3), δ: 47.6 (d, C(4´), 2J = 10.1 Hz); 47.8
(d, C(5´), 2J = 9.9 Hz); 73.4 (s, CHO); 74.1 (s, CHO); 116.5
(d, CHPh, 3J = 12.0 Hz); 120.2 (s, CHPh); 121.6 (s, CHNaphthyl);
125.0 (s, CHNaphthyl); 125.7 (s, CHNaphthyl); 126.9 (s, CNaphthyl);
127.2 (s, CHNaphthyl); 127.7 (s, CHNaphthyl); 128.4 (s, CHNaphthyl);
129.2 (s, CHPh); 129.8 (s, CHNaphthyl); 132.0 (s, CNaphthyl); 136.8
(s, CNaphthyl); 147.3 (d, CPh,
2J = 16.0 Hz); 174.8 (s, C=O);
This work was financially supported by the Russian
Foundation for Basic Research (Project No. 08ꢀ03ꢀ00416ꢀa)
and the Council on Grants at the President of the Russian
Federation (State Support Program for young Russian
Ph.D. scientists, Grant MKꢀ3889.2010.3).
175.2 (s, C=O). 1H NMR (CDCl3), δ: 3.67 (m, 4 H); 3.82 (m, 4 H);
4.74 (m, 1 H); 4.78 (m, 1 H); 6.94 (m, 4 H); 7.06 (t, 1 H,
J = 8.0 Hz); 7.14 (m, 6 H); 7.21 (m, 3 H); 7.23—7.41 (m, 9 H);
7.48 (m, 2 H); 7.84 (t, 1 H, J = 8.4 Hz); 7.90 (m, 1 H).
IR (CHCl3), ν/cm–1: 1732 (C=O). MS (MALDI TOF/TOF),
m/z (Irel (%)): 761 (23) [M + Na]+, 739 (100) [M + H]+.
References
Asymmetric allylic amination of (E)ꢀ1,3ꢀdiphenylallyl acetate
(6) with pyrrolidine. A solution of [Pd(allyl)Cl]2 (0.0037 g,
0.01 mmol) and an appropriate ligand (0.02 or 0.04 mmol) in an
appropriate solvent (5 mL) was stirred for 40 min. Then (E)ꢀ1,3ꢀ
diphenylallyl acetate (0.1 mL, 0.5 mmol) was added. The resultꢀ
1. J. M. Brown, in Comprehensive Asymmetric Catalysis, Eds
E. N. Jacobsen, A. Pfaltz, Y. Yamamoto, Springer, Berlin,
1999, Vol. 1, pp. 121—182.

Asymmetric allylation
Russ.Chem.Bull., Int.Ed., Vol. 59, No. 6, June, 2010
1247
2. T. Ohkuma, M. Kitamura, R. Noyori, in Catalytic Asymꢀ
metric Synthesis, Ed. I. Ojima, WileyꢀVCH, New York, 2000,
pp. 1—110.
3. M. J. Burk, Acc. Chem. Res., 2000, 33, 363.
4. H.ꢀU. Blaser, E. Schmidt, Asymmetric Catalysis on Industrial
Scale, WileyꢀVCH, Weinheim, 2004.
B. Schäffner, A. Börner, S. Rosset, G. Bailat, A. Alexakis,
Eur. J. Org. Chem., 2009, 3923.
29. G. Buono, N. Toselli, D. Martin, in Phosphorus Ligands in
Asymmetric Catalysis, Ed. A. Börner, WileyꢀVCH, Weinheim,
2008, Vol. 2, pp. 529—546.
30. M. T. Reetz, H. Oka, R. Goddard, Synthesis, 2003, 1809.
31. S. Enthaler, G. Erre, K. Junge, D. Addis, R. Kadyrov,
M. Beller, Chem. Asian J., 2008, 3, 1104.
5. I. P. Beletskaya, M. M. Kabachnik, Mendeleev Commun.,
2008, 18, 113.
6. C. A. Falciola, A. Alexakis, Eur. J. Org. Chem., 2008, 3765.
7. G. C. Hargaden, P. J. Guiry, Chem. Rev., 2009, 109, 2505.
8. J. Ansel, M. Wills, Chem. Soc. Rev., 2002, 31, 259.
9. A. Alexakis, C. Benhaim, Eur. J. Org. Chem., 2002, 19, 3221.
10. O. Molt, T. Shrader, Synthesis, 2002, 2633.
11. K. N. Gavrilov, O. G. Bondarev, A. I. Polosukhin, Usp.
Khim., 2004, 73, 726 [Russ. Chem. Rev. (Engl. Transl.), 2004,
73, 671].
32. D. Sanhes, A. Gual, S. Castillon, C. Claver, M. Gomez,
E. Teuma, Tetrahedron: Asymmetry, 2009, 20, 1009.
33. K. N. Gavrilov, S. V. Zheglov, E. B. Benetsky, A. S. Saꢀ
fronov, E. A. Rastorguev, N. N. Groshkin, V. A. Davankov,
B. Schäffner, A. Börner, Tetrahedron: Asymmetry, 2009,
20, 2490.
34. K. V. L. Crepy, T. Imamoto, Adv. Synth. Catal., 2003, 345, 79.
35. B. M. Trost, M. L. Crawley, Chem. Rev., 2003, 103, 2921.
36. T. Graening, H.ꢀG. Schmalz, Angew. Chem., Int. Ed., 2003,
42, 2580.
12. M. T. Reetz, G. Mehler, A. Meiswinkel, T. Sell, Tetrahedron
Lett., 2002, 43, 7941.
13. J. M. Brunel, Chem. Rev., 2005, 105, 857.
14. M. Dieguez, O. Pamies, Acc. Chem. Res., 2010, 43, 312.
15. M. Yan, Z.ꢀY. Zhou, A. S. C. Chan, Chem. Commun.,
2000, 115.
37. Z. Lu, S. Ma, Angew. Chem., Int. Ed., 2008, 47, 258.
38. A. M. d´A. R. Gonsalves, M. E. S. Serra, D. Murtinho, V. F.
Silva, A. M. Beja, J. A. Paixao, M. R. Silva, L. A. da Veiga,
J. Mol. Catal. A: Chem., 2003, 195, 1.
16. L. Liang, A. S. C. Chan, Tetrahedron: Asymmetry, 2002,
13, 1393.
39. J. M. Brunel, T. Constantieux, G. Buono, J. Org. Chem.,
1999, 64, 8940.
17. L. Liang, T. T.ꢀL. AuꢀYeung, A. S. C. Chan, Org. Lett.,
2002, 4, 3799.
40. H. Arzoumanian, G. Buono, M. Choukrad, J.ꢀF. Petrigꢀ
nani, Organometallics, 1988, 7, 59.
18. L. Su, X. Li, W. L. Chan, X. Jia, A. S. C. Chan, Tetrahedron:
Asymmetry, 2003, 14, 1865.
19. L. Liang, M. Yan, Y.ꢀM. Li, A. S. C. Chan, Tetrahedron:
Asymmetry, 2004, 15, 2575.
41. M. Kimura, Y. Uozumi, J. Org. Chem., 2007, 72, 707.
42. C. J. Ngono, T. Constantieux, G. Buono, Eur. J. Org. Chem.,
2006, 1499.
43. T. Jerphagnon, J.ꢀL. Renaud, C. Bruneau, Tetrahedron:
Asymmetry, 2004, 15, 2101.
44. K. Barta, M. Holscher, G. Francio, W. Leitner, Eur. J. Org.
Chem., 2009, 4102.
45. C. A. Tolman, Chem. Rev., 1977, 77, 313.
46. A. I. Polosukhin, A. Yu. Kovalevskii, K. N. Gavrilov, Koord.
Khim., 1999, 25, 812 [Russ. J. Coord. Chem. (Engl. Transl.),
1999, 25, 758].
47. Y. Mata, M. Dieguez, O. Pamies, C. Claver, Adv. Synth.
Catal., 2005, 347, 1943.
48. M. R. Marre, M. Sanchez, J. F. Brazier, R. Wolf, J. Bellan,
Can. J. Chem., 1982, 60, 456.
49. P. R. Auburn, P. B. McKenzie, B. Bosnich, J. Am. Chem.
Soc., 1985, 107, 2033.
50. J.ꢀP. Genet, S. Juge, S. Achi, S. Mallart, J. R. Montes,
G. Levif, Tetrahedron, 1988, 44, 5263.
20. S. J. Sturla, S. L. Buchwald, J. Org. Chem., 2002, 67, 3398.
21. C. J. Cobley, R. D. J. Froese, J. Klosin, C. Qin, G. T. Whiteꢀ
ker, K. A. Abboud, Organometallics, 2007, 26, 2986.
22. Y. Zou, Y. Yan, X. Zhang, Tetrahedron Lett., 2007, 48, 4781.
23. V. N. Tsarev, S. E. Lyubimov, A. A. Shiryaev, S. V. Zheglov,
O. G. Bondarev, V. A. Davankov, A. A. Kabro, S. K. Moiꢀ
seev, V. N. Kalinin, K. N. Gavrilov, Eur. J. Org. Chem.,
2004, 2214.
24. 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.
25. K. N. Gavrilov, S. E. Lyubimov, O. G. Bondarev, M. G.
Maximova, S. V. Zheglov, P. V. Petrovskii, V. A. Davankov,
M. T. Reetz, Adv. Synth. Catal., 2007, 349, 609.
26. K. N. Gavrilov, S. V. Zheglov, P. A. Vologzhanin, M. G.
Maximova, A. S. Safronov, S. E. Lyubimov, V. A. Davanꢀ
kov, B. Schäffner, A. Börner, Tetrahedron Lett., 2008,
49, 3120.
51. K. N. Gavrilov, S. E. Lyubimov, S. V. Zheglov, E. B.
Benetsky, V. A. Davankov, J. Mol. Catal. A, 2005, 231, 255.
52. S. E. Lyubimov, V. A. Davankov, K. N. Gavrilov, Tetraꢀ
hedron Lett., 2006, 47, 2721.
27. K. N. Gavrilov, S. V. Zheglov, P. A. Vologzhanin, E. A.
Rastorguev, A. A. Shiryaev, M. G. Maximova, S. E. Lyubiꢀ
mov, E. B. Benetsky, A. S. Safronov, P. V. Petrovskii, V. A.
Davankov, B. Schäffner, A. Börner, Izv. Akad. Nauk,
Ser. Khim., 2008, 2266 [Russ. Chem. Bull., Int. Ed., 2008,
57, 2311].
53. O. Pamies, M. Dieguez, Chem. Eur. J., 2008, 14, 944.
54. A. Frolander, S. Lutsenko, T. Privalov, C. Moberg, J. Org.
Chem., 2005, 70, 9882.
28. K. N. Gavrilov, E. B. Benetsky, T. B. Grishina, E. A. Rasꢀ
torguev, M. G. Maksimova, S. V. Zheglov, V. A. Davankov,
Received December 24, 2009;
in revised form March 30, 2010