Phosphorodiamidite derivatives of 1,1'-bi-2-naphthol containing stereogenic phosphorus atoms as ligands in enantioselective catalysis

Article abstract of DOI:10.1007/s11172-010-0097-0

P*-Mono- and P*,P*-bidentate phosphorodiamidites containing the (S_a)-1,1'-binaphthyl core and 1,3,2-diazaphospholidine rings were synthesized. The use of these compounds in the rhodium-catalyzed asymmetric hydrogenation, as well as in the palla

Full text of DOI:10.1007/s11172-010-0097-0

434
Russian Chemical Bulletin, International Edition, Vol. 59, No. 2, pp. 434—440, February, 2010
Phosphorodiamidite derivatives of 1,1´ꢀbiꢀ2ꢀnaphthol containing stereogenic
phosphorus atoms as ligands in enantioselective catalysis
K. N. Gavrilov,a A. S. Safronov, E. A. Rastorguev, N. N. Groshkin, S. V. Zheglov,
b
a
a
a
a
a
b
b
c
A. A. Shiryaev, M. G. Maksimova, P. V. Petrovskii, V. A. Davankov, and M. T. Reetz
aS. A. Esenin Ryazan State Pedagogic University,
4
6 ul. Svobody, 390000 Ryazan, Russian Federation.
Fax: +7 (491 2) 77 5498. Eꢀmail: k.gavrilov@rsu.edu.ru
A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences,
8 ul. Vavilova, 119991 Moscow, Russian Federation.
b
2
Fax: +7 (495) 135 6471. Eꢀmail: vxd2000@mail.ru
c
MaxꢀPlanckꢀInstitute For Coal Research,
1
KaiserꢀWilhelmꢀPlatz, 45470 Mülheim an der Ruhr, Germany.*
Fax: (49 208) 306 2985. Eꢀmail: reetz@mpiꢀmuelheim.mpg.de
P*ꢀMonoꢀ and P*,P*ꢀbidentate phosphorodiamidites containing the (S )ꢀ1,1´ꢀbinaphthyl
a
core and 1,3,2ꢀdiazaphospholidine rings were synthesized. The use of these compounds in the
rhodiumꢀcatalyzed asymmetric hydrogenation, as well as in the palladiumꢀ and platinumꢀ
catalyzed asymmetric alkylation and amination, resulted in the formation of the products with
ee of up to 99%.
Key words: P*ꢀchiral phosphorodiamidites, rhodium complexes, palladium complexes,
platinum complexes, catalysts, asymmetric allylation, asymmetric hydrogenation.
The modern asymmetric metal complex catalysis is
phite ligands LA—C containing the 1,3,2ꢀdioxaphosphepꢀ
ine rings based on BINOL, its octahydrogenated derivaꢀ
one of the most effective and environmentally safe methꢀ
ods for the synthesis of optically pure organic and heteroꢀ
organic compounds. In addition to the wellꢀknown appliꢀ
cation in pharmaceutical chemistry, this method is sucꢀ
cessfully used in the synthesis of fragrance compounds,
plant protection chemicals, individual stereoisomeric polyꢀ
mers, and liquid crystals.1 To achieve virtually quantiꢀ
tative chemical and optical yields in enantioselective catꢀ
alytic transformations, it is necessary to carefully optiꢀ
mize various reaction parameters, primarily, to correctly
choose the corresponding ligand group and to rationally
tive (H ꢀBINOL), or various 2,2´ꢀdihydroxyꢀ1,1´ꢀbipheꢀ
8
nyls were successfully used in the Cuꢀcatalyzed conjugatꢀ
1
3—17
ed addition,
the Coꢀcatalyzed Pauson–Khand reacꢀ
1
8
19,20
tion, and the Rhꢀcatalyzed hydroformylation.
Phosꢀ
phites LD—F containing the 1,3,2ꢀdioxaphosphorinane and
1,3,2ꢀdioxaphospholane rings based on chiral 1,3ꢀ and
1,2ꢀdiols appeared to be ineffective stereoselectors. Thus,
the ee of no higher than 40% was achieved with their use in
—4
2
1—23
the Rhꢀcatalyzed hydroformylation of styrene.
Hence, the synthesis of new effective phosphiteꢀtype
5
design each representative of this group. P,PꢀBidentate
BINOLꢀbased P,Pꢀbidentate ligands remains an imporꢀ
2
4,25
phosphines belong to a class of effective phosphorusꢀconꢀ
taining stereoselectors. At the same time, recent studies
tant problem. Previously,
we have described the synꢀ
thesis of diastereomeric P*,P*ꢀbidentate phosphorodiꢀ
amidites containing 1,3,2ꢀdiazaphospholidine rings based
on 1,4:3,6ꢀdianhydroꢀDꢀmannite and reported on the use
of these compounds in catalytic asymmetric reactions. It
should be noted that P*ꢀchiral 1,3,2ꢀdiazaphospholidines
belong to an attractive group of optically active phosphoroꢀ
diamidite ligands. In particular, these ligands have balꢀ
anced electronic characteristics because they are both good
πꢀacceptors (due to the accessibility of lowꢀlying π*PN
orbitals) and good σꢀdonors. The inclusion of the phosꢀ
phorus atom in the fiveꢀmembered ring enhances the reꢀ
sistance of the ligands to oxidation and hydrolysis, and the
6
—11
have shown
that phosphiteꢀtype P,Pꢀbidentate ligands
are highly competitive with the aboveꢀmentioned comꢀ
pounds and have advantages in that they can easily be
synthesized from readily accessible precursors, are resisꢀ
tant to oxidation, have a pronounced πꢀacidity, and are
less expensive. In particular, bisꢀphosphite derivatives of
the known chiral agent 1,1´ꢀbiꢀ2ꢀnaphthol (BINOL) can
be considered as promising stereoinducers.12 Thus, phosꢀ
*
MaxꢀPlanckꢀInstitut für Kohlenforschung, 1 KaiserꢀWilhelmꢀ
Platz, 45470 Mülheim an der Ruhr, Germany.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 425—430, February, 2010.
066ꢀ5285/10/5902ꢀ0434 © 2010 Springer Science+Business Media, Inc.
1

Phosphorodiamidite derivatives of BINOL
Russ.Chem.Bull., Int.Ed., Vol. 59, No. 2, February, 2010
435
possibility of varying the nature of the substituents at the
nitrogen atoms allows the control over the steric and elecꢀ
tronic parameters.2
In the present study, we report the synthesis of the first
P*,P*ꢀbidentate phosphorodiamidite 1 containing the
selective hydrogenation with the use of inexpensive moꢀ
lecular hydrogen and a small amount of a catalyst holds
considerable promise for the industrial use. The allylic
substitution, which is tolerant to various functional groups
in the substrate and operates with a wide range of Cꢀ, Nꢀ,
Oꢀ, Sꢀ, and Pꢀnucleophiles, is successfully used in the key
6,27
(
Sa)ꢀ1,1´ꢀbinaphthyl core and 1,3,2ꢀdiazaphospholidine
2
8—31
rings and the application of this compound in the enantioꢀ
selective catalysis. We also compared the performance
characteristics of phosphorodiamidite 1 with those of the
specially synthesized related P*ꢀmonodentate ligand 2
containing the pivalate moiety (S)ꢀBINOL as the exocyꢀ
clic substituent. We investigated the asymmetric hydrogeꢀ
nation and allylation as catalytic reactions. The enantioꢀ
steps of the synthesis of various natural compounds.
Results and Discussion
New P*ꢀchiral phosphorodiamidites 1 and 2 were synꢀ
thesized by the oneꢀstep phosphorylation of (S)ꢀBINOL 3
or its pivalate 4 by reagent 5 in toluene (Scheme 1).
Scheme 1

436
Russ.Chem.Bull., Int.Ed., Vol. 59, No. 2, February, 2010
Gavrilov et al.
It should be noted that phosphorylating agent 5 can
Table 1. Results of the Rhꢀcatalyzed hydrogenation of substrates
6 and 7а
3
2
easily be synthesized in high yield from readily accessiꢀ
3
3,34
ble (S)ꢀglutamic acid anilide.
Compound 1 is an indiꢀ
Run
Ligand (L)
L/Rh
Substrate
ee (%)b,c
vidual stereoisomer, whereas compound 2 is a mixture of
epimers with respect to the phosphorus stereocenter. This
is evident from the fact that the 3 P NMR spectra of these
(
configuration)
1
1
2
3
4
5
6
1
1
2
1
1
2
1
2
2
1
2
2
6
6
6
7
7
7
>99 (R)
98 (R)
49 (R)
99 (S)
97 (S)
35 (S)
compounds in CDCl show one singlet at δ 128.7 and
3
P
two singlets at δ 129.7 (73%) and 119.6 (27%), respecꢀ
P
tively. Ligand 1 and the major epimer of ligand 2 have the
13
P* stereocenters in the (R) configuration. The C NMR
spectra of these ligands are characterized by large spinꢀ
2
spin coupling constants J
(36.5 and 32.7 Hz), which
а
C(8″),P
The reaction conditions: 25 °C, CH Cl , 20 h, 0.5 mol.%
2 2
are indicative of the cis orientation of the phosphorus lone
pair with respect to the C(8″) atom. The pseudoequatoriꢀ
ally oriented exocyclic substituent at the phosphorus atom
and the pyrrolidine ring of the phosphabicyclo[3.3.0]ꢀ
octane core are in the trans arrangement. On the contrary,
the minor epimer of ligand 2 contains the asymmetric
phosphorus atom in the (S) configuration, as evidenced by
[
Rh(COD) ]BF , P = 1.3 atm; in all cases, the conversion
2 4 H2
was 100%.
b
The conversion of substrate 6 and the enantiomeric excesses of
product 8 were determined by GC (Lipodex E, 25 m × 0.25 mm,
–
1
8
0 °C, 1 mL min ) or HPLC (Daicel Chiralcel ODꢀH,
i
–1
C H : Pr OH = 98 : 2, 0.8 mL min , 220 nm, t(R) = 9.1 min,
t(S) = 16.1 min).
c
6
14
The conversion of substrate 7 and the enantiomeric excesses of
13
the fact that the C NMR spectrum of 2 has the small
product 9 were determined by GC (XEꢀvaline(tertꢀbutylamide),
4×0.25 mm, 85 °C, 1 mL min ).
2
32,34—38
constant J
= 3.8 Hz.
Compounds 1 and 2
–1
C(8″),P
are rather stable in air, can be stored over a long period of
time under a dry atmosphere, and are readily soluble in
usual organic media.
P*,P*ꢀbidentate phosphorodiamidites based on 1,4:3,6ꢀ
dianhydroꢀDꢀmannite show an analogous behavior. These
compounds also provide the much higher asymmetric inꢀ
duction. In this respect, P*ꢀchiral 1,3,2ꢀdiazaphosphoꢀ
lidines substantially differ from known BINOLꢀbased axiꢀ
ally chiral 1,3,2ꢀdioxaꢀ and 1,3,2ꢀoxazaphosphepines,
where Pꢀmonoꢀ and P,Pꢀbidentate ligands are equally
effective in most cases.
In the next step, stereoselectors 1 and 2 were studied
in the Pdꢀ and Ptꢀcatalyzed asymmetric allylation of (E)ꢀ
In the first step of the catalytic experiments, phosphoꢀ
rodiamidites 1 and 2 were used in the Rhꢀcatalyzed asymꢀ
metric hydrogenation of prochiral methyl esters of unsatꢀ
urated acids, viz., dimethyl itaconate (6) and methyl
Nꢀacetylaminoacrylate (7) (Scheme 2, Table 1). The comꢀ
plex [Rh(COD) ]BF (COD is 1,5ꢀcyclooctadiene) was
2
5
2
4
3
9,40
used as the precatalyst.
Scheme 2
1
,3ꢀdiphenylallyl acetate (10) (Scheme 3, Tables 2 and 3).
Scheme 3
Cat is a catalyst
P*,P*ꢀBidentate ligand 1 provides the virtually quanꢀ
titative enantioselectivity (ее 97—99%) regardless of the
nature of the starting substrate and the L/Rh molar ratio
(
see Table 1, runs 1, 2, 4, and 5). At the same time,
The Pdꢀcatalyzed allylic alkylation of substrate 10 with
P*ꢀmonodentate stereoselector 2 allows the synthesis of
products 8 and 9 having the same absolute configuration
as in the reactions with the involvement of ligand 1 but
with a substantially lower optical purity (ее 49 and 35%,
respectively) (see Table 1, runs 3 and 6). P*ꢀMonoꢀ and
dimethyl malonate with the use of ligand 1 affords product
(S)ꢀ11 (ee up to 99%). The higher enantioselectivity is
observed in THF; the highest conversions is achieved in
CH Cl (see Table 2, runs 1—4). The optimal L/Pd molar
2
2
ratio is 1, whereas an increase in this ratio to 2 leads to

Phosphorodiamidite derivatives of BINOL
Russ.Chem.Bull., Int.Ed., Vol. 59, No. 2, February, 2010
437
Table 2. Results of the Pdꢀ and Ptꢀcatalyzed allylic alkylation of substrate 10 with dimethyl
malonateа
Run
Source of
Pd or Pt
Ligand
(L)
L/Pd
(L/Pt)
Solvent
Converꢀ
sion (%)
ee (%)b
(configuration)
1
2
3
4
5
6
7
8
9
[Pd(All)Cl]2
[Pd(All)Cl]2
[Pd(All)Cl]2
[Pd(All)Cl]2
[Pt(All)Cl]4
[Pt(All)Cl]4
[Pt(All)Cl]4
[Pt(All)Cl]4
[Pd(All)Cl]2
[Pd(All)Cl]2
[Pd(All)Cl]2
[Pd(All)Cl]2
1
1
1
1
1
1
1
1
2
2
2
2
1
2
1
2
1
2
1
2
1
2
1
2
THF
THF
57
65
94
93
56
54
73
61
90
83
72
100
99 (S)
92 (S)
94 (S)
65 (S)
60 (R)
72 (R)
87 (R)
85 (R)
29 (S)
40 (S)
41 (S)
20 (S)
CH Cl
2
2
2
CH Cl
2
THF
THF
CH Cl
2
2
2
CH Cl
2
THF
THF
10
11
12
CH Cl
2
2
2
CH Cl
2
а
b
The reaction conditions: 20 °C, 48 h, 2 mol.% [Pd(All)Cl] or 1 mol.% [Pt(All)Cl] .
2
4
The conversion of substrate 10 and the enantiomeric excesses of product 11 were determined by
i
–1
HPLC (Daicel Chiralcel ODꢀH, C H : Pr OH = 99 : 1, 0.6 mL min , 254 nm).
6
14
a decrease in the asymmetric induction, particularly,
in the reaction performed in CH Cl . Like the asymꢀ
selectivity in CH Cl , and product 11 has the (R) conꢀ
figuration.
2
2
2
2
metric hydrogenation, the experiments with the use of
P*ꢀmonodentate ligand 2 afforded the reaction product
having the same absolute configuration and low optical
purity (ее is at most 41%) (see Table 2, runs 9—12). In the
presence of the platinum catalyst, phosphorodiamidite 1
provides a somewhat lower enantioselectivity (ee is no
higher than 87%) (see Table 2, runs 5—8), but it is comꢀ
parable to that of the effective P,Nꢀ and P,Pꢀbidentate
The Pdꢀcatalyzed allylic amination of (E)ꢀ1,3ꢀdipheꢀ
nylallyl acetate (10) with pyrrolidine with the use of P*,P*ꢀ
bidentate ligand 1 gives product (R)ꢀ12 in high optical
yields (96—99%) (see Scheme 3 and Table 3, runs 1—4)
regardless of the L/Pd molar ratio and the nature of the
solvent, the highest conversion being observed in CH Cl .
It is interesting that P*ꢀmonodentate ligand 2 is also an
excellent stereoinducer. Thus, the ее of up to 99% was
achieved in the reactions with this ligand (see Table 3,
runs 9—12). It should be noted that P*ꢀmonodentate
ligands based on 1,4:3,6ꢀdianhydroꢀDꢀmannite are virtuꢀ
2
2
4
1,42
phosphine stereoselectors PHOX and CHIRAPHOS.
It should be noted that the Ptꢀcatalyzed alkylation of
substrate 10 results in the higher conversion and enantioꢀ
Table 3. Results of the Pdꢀ and Ptꢀcatalyzed allylic amination of substrate 10 with pyrrolidineа
Run
Source of
Pd or Pt
Ligand
(L)
L/Pd
(L/Pt)
Solvent
Converꢀ
sion(%)
ee (%)b
(configuration)
1
2
3
4
5
6
7
8
9
[Pd(All)Cl]2
[Pd(All)Cl]2
[Pd(All)Cl]2
[Pd(All)Cl]2
[Pt(All)Cl]4
[Pt(All)Cl]4
[Pt(All)Cl]4
[Pt(All)Cl]4
[Pd(All)Cl]2
[Pd(All)Cl]2
[Pd(All)Cl]2
[Pd(All)Cl]2
1
1
1
1
1
1
1
1
2
2
2
2
1
2
1
2
1
2
1
2
1
2
1
2
THF
THF
48
68
100
90
100
100
100
100
98
96 (R)
98 (R)
98 (R)
99 (R)
83 (S)
50 (S)
86 (S)
84 (S)
89 (R)
88 (R)
99 (R)
73 (R)
CH Cl
2
2
2
CH Cl
2
THF
THF
CH Cl
2
2
2
CH Cl
2
THF
THF
10
11
12
32
96
100
CH Cl
2
2
2
CH Cl
2
а
b
The reaction conditions: 20 °C, 48 h, 2 mol.% [Pd(All)Cl] or 1 mol.% [Pt(All)Cl] .
2
4
The conversion of substrate 10 and the enantiomeric excesses of product 12 were determined by
i
–1
HPLC (Daicel Chiralcel ODꢀH, ODꢀH, C H : Pr OH : HNEt = 200 : 1 : 0.1, 0.9 mL min
,
6
14
2
2
54 nm).

438
Russ.Chem.Bull., Int.Ed., Vol. 59, No. 2, February, 2010
Gavrilov et al.
ally as effective in this reaction as P*,P*ꢀbidentate anaꢀ
onate and the amination of 10 with pyrrolidine were performed,
and the conversions and the optical yields of products 11 and 12
were determined according to procedures described in the literꢀ
ature.3
logs.25 The Ptꢀcatalyzed amination of compound 10 with
pyrrolidine is characterized by the quantitative conversion
of the starting substrate and the good enantioselectivity of
the formation of product (S)ꢀ12 (up to 86%). The nature
of the solvent has virtually no effect on the asymmetric
induction, and the optimal L/Pt molar ratio is 1 (see
Table 3, runs 5—8).
2,48
(
S)ꢀBINOL (3), dimethyl itaconate (6), methyl 2ꢀ(Nꢀacetylꢀ
amino)acrylate (7), dimethyl malonate, and N,Oꢀbis(trimethylꢀ
silyl)acetamide (BSA) are commercial products (Fluka and Alꢀ
drich).
2,2´ꢀBis[(2R,5S)ꢀ3ꢀphenylꢀ1,3ꢀdiazaꢀ2ꢀphosphabicycloꢀ
To sum up all the aboveꢀconsidered data, the followꢀ
ing conclusions can be drawn. P*,P*ꢀBidentate phosphoꢀ
rodiamidite 1 is a substantially better stereoselector than
P*ꢀmonodentate ligand 2 in the Rhꢀcatalyzed asymmetꢀ
ric hydrogenation and the Pdꢀcatalyzed allylic alkylation,
whereas these ligands are equally effective in the Pdꢀcataꢀ
[3.3.0]octꢀ2ꢀyloxy]ꢀ(S )ꢀ1,1´ꢀbinaphthyl (1). A solution of
a
(S)ꢀBINOL (1.43 g, 5 mmol) in toluene (17 mL) was added
dropwise with vigorous stirring to a solution of (2R,5S)ꢀ2ꢀchloꢀ
roꢀ3ꢀphenylꢀ1,3ꢀdiazaꢀ2ꢀphosphabicyclo[3.3.0]octane (5) (2.41 g,
1
2
2
0 mmol) and Et N (1.45 mL, 10.4 mmol) in toluene (26 mL) at
0 °C for 30 min. The reaction solution was stirred at 20 °C for
3
4 h, and then Et N•HCl was removed by filtration. The filtrate
3
4
1,42
lyzed allylic amination. In addition to the studies,
we
was concentrated in vacuo (40 Torr). The product was purified
by column chromatography on silica gel using a 1 : 1 hexꢀ
ane—AcOEt mixture as the eluent. The yield was 2.92 g (84%),
white powder, m.p. 144—145 °C, [α]20 +171.4 (c 1.0, CH Cl ).
describes the third example of the successful use of phosꢀ
phorusꢀcontaining ligands in the Ptꢀcatalyzed asymmetꢀ
ric allylic alkylation. We also report the first example of
the use of this ligands in the Ptꢀcatalyzed asymmetric
allylic amination.31 The allylic substitution in the presꢀ
ence of palladium and platinum catalysts affords products
having the opposite absolute configurations, all other conꢀ
ditions being the same.
D
2
2
Found (%): C, 72.88; H, 5.86; N, 7.93. C42H40N4O2P2. Calcuꢀ
1
3
lated (%): C, 72.61; H, 5.80; N, 8.06. C NMR (CDCl ), δ: 25.6
3
3
2
(
5
1
3
d, C(7″), J = 4.4 Hz), 31.3 (s, C(6″)), 47.1 (d, C(8″), J = 36.5 Hz),
3.8 (d, C(4″), J = 8.0 Hz), 62.3 (d, C(5″), 2J = 8.8 Hz),
14.9 (d, CHPh, J = 12.4 Hz), 118.7 (s, CHPh), 123.1 (d, CHAr
J = 5.1 Hz), 123.6 (s, CH ), 124.5 (s, C ), 125.3 (s, CH ),
2
3
,
Ar
Ar
Ar
1
27.0 (s, CHAr), 127.6 (s, CHAr), 128.4 (s, CHAr), 128.8
Experimental
2
(
s, CHPh), 130.1 (s, CAr), 134.1 (s, C ), 145.2 (d, C , J =
Ar Ph
16.1 Hz), 150.1 (d, CAr, 2J = 8.0 Hz). H NMR (CDCl ), δ:
1
=
3
The 31P, 1H, and 13C NMR spectra were measured on
a Bruker AMXꢀ400 instrument (161.98, 400.13, and 100.61 MHz,
1.37 (dq, 2 H, J = 11.8 Hz); 1.50 (m, 4 H); 1.68 (dq, 2 H,
J = 11.8 Hz); 2.53 (ddd, 2 H, J = 8.2 Hz, J = 7.1 Hz, J = 5.9 Hz);
2.90 and 3.40 (both m, 4 H each); 6.65 (d, 4 H, J = 7.8 Hz); 6.71
(t, 4 H, J = 7.9 Hz); 7.02 (t, 4 H, J = 8.5 Hz); 7.16 (m, 4 H); 7.36
(d, 2 H, J = 7.7 Hz, J = 7.3 Hz; 7.74 (d, 4 H, J = 8.3 Hz). EI MS,
31
respectively) with respect to 85% H PO in D O ( P) and Me Si
3
4
2
4
1
13
13
(
H and C). The assignment of the signals in the C NMR
spectra was made with the use of the DEPT technique. The EI
mass spectra (70 eV) were measured on a Varian MATꢀ311 inꢀ
strument. The matrixꢀassisted laser desorption ionization timeꢀ
ofꢀflight (MALDI TOF/TOF) mass spectra were obtained
on a Bruker Daltonics Ultraflex instrument. The IR spectra
+
m/z (Irel (%)): 695 [M] (2). MALDI TOF/TOF MS, m/z
+
+
(Irel (%)): 718 [M + Na] (100), 696 [M + H] (28).
2ꢀ[(2R,5S)ꢀ3ꢀPhenylꢀ1,3ꢀdiazaꢀ2ꢀphosphabicyclo[3.3.0]ꢀ
octꢀ2ꢀyloxy]ꢀ2´ꢀpivaloyloxyꢀ(S )ꢀ1,1´ꢀbinaphthyl (2). A solution
a
were recorded on a Specord Mꢀ80 instrument in CHCl in poꢀ
of (S)ꢀ2ꢀpivaloyloxyꢀ2´ꢀhydroxyꢀ1,1´ꢀbinaphthyl (4) (1.85 g,
3
lyethylene cells. The enantiomeric analysis of the catalytic reꢀ
action products was performed by HPLC on an HP Agilent
5 mmol) and Et N (0.73 mL, 5.2 mmol) in toluene (15 mL) was
3
added dropwise with vigorous stirring to a solution of (2R,5S)ꢀ2ꢀ
chloroꢀ3ꢀphenylꢀ1,3ꢀdiazaꢀ2ꢀphosphabicyclo[3.3.0]octane (5)
(1.2 g, 5 mmol) in toluene (15 mL) at 20 °C for 20 min. The
reaction mixture was heated to reflux and then cooled to 20 °C,
1
100 chromatograph. The optical rotation was measured on
a SMꢀ3 polarimeter. The specific rotation is expressed in
–
1
(
deg mL) (g dm) ; the concentrations of the solutions are exꢀ
–
1
pressed in g (100 mL) . The elemental analysis was performed
at the Laboratory of Organic Microanalysis of the A. N. Nesmeꢀ
yanov Institute of Organoelement Compounds of the Russian
Academy of Sciences.
Et N•HCl was removed by filtration, and the filtrate was conꢀ
3
centrated in vacuo (40 Torr). The product was purified by colꢀ
umn chromatography on silica gel using a 1 : 1 hexane—AcOEt
mixture as the eluent. The yield was 2.04 g (71%), white powder,
m.p. 59—60 °C, [α]20 +83.8 (c 1.0, CH Cl ). Found (%):
All reactions were carried out under dry argon in anhydrous
solvents. (2R,5S)ꢀ2ꢀChloroꢀ3ꢀphenylꢀ1,3ꢀdiazaꢀ2ꢀphosphaꢀ
bicyclo[3.3.0]octane (5), (S)ꢀ2ꢀpivaloyloxyꢀ2´ꢀhydroxyꢀ1,1´ꢀbiꢀ
naphthyl (4), and the complexes [Rh(COD) ]BF , [Pd(All)Cl] ,
D
2
2
C, 75.45; H, 6.08; N, 4.99. C H N O P. Calculated (%): C, 75.24;
3
6
35
2 3
13
3
H, 6.14; N, 4.87. C NMR (CDCl ), δ: 26.0 (d, C(7″), J =
3
= 3.8 Hz), 26.2, 26.3 (s, CH ), 31.0 (s, C(6″)), 38.5 (s, C), 47.1
2
4
2
3
2
2
and [Pt(All)Cl] were synthesized according to known proceꢀ
(d, C(8″), J = 32.7 Hz), 53.1 (d, C(4″), J = 6.8 Hz), 62.0
(d, C(5″), J = 8.0 Hz), 115.0 (d, CH , J = 12.4 Hz), 118.2
4
dures.3
2,43—46
2
3
Ph
The starting substrate, viz., (E)ꢀ1,3ꢀdiphenylallyl acetate
(s, CHPh), 120.5 (s, CH ), 122.7 (s, CH ), 122.9 (s, CH ), 123.6
Ar
Ar
Ar
(
10), was synthesized according to a procedure described previꢀ
(s, CH ), 123.9 (s, CAr), 124.0 (s, CHAr), 124.9 (s, CH ), 125.7
Ar Ar
4
5
ously. The catalytic experiments on the asymmetric hydrogeꢀ
nation of substrates 6 and 7 were carried out, and the converꢀ
sions and the optical yields of products 8 and 9 were determined
according to known procedures.47 The catalytic experiments on
the asymmetric alkylation of substrate 10 with dimethyl malꢀ
(s, CH ), 125.8 (s, CH ), 126.2 (s, CH ), 127.4 (s, CH ),
Ar Ar Ar Ar
127.7 (s, CHAr), 128.3 (s, CH ), 128.7 (s, CH ), 128.9 (s, C ),
Ar
Ph
Ar
129.2 (s, C ), 130.9 (s, C ), 133.5 (s, C ), 133.9 (s, C ), 146.0
Ar
Ar
Ar
,
Ar
2
2
(d, CPh
,
J = 17.7 Hz), 151.0 (d, CAr
J = 5.1 Hz), 154.6
(s, C ), 176.1 (s, C=O) (major epimer) and 26.4, 26.5 (s, CH ),
Ar
3

Phosphorodiamidite derivatives of BINOL
Russ.Chem.Bull., Int.Ed., Vol. 59, No. 2, February, 2010
439
2
2
=
7.3 (s, C(7″)), 31.6 (s, C(6″)), 38.3 (s, C), 43.0 (d, C(8″), J =
substrate 10 and the optical yields of product 12 were deterꢀ
mined by HPLC on chiral stationary phases.
2
2
3.8 Hz), 51.0 (d, C(4″), J = 6.5 Hz), 65.2 (d, C(5″), J = 10.7 Hz),
17.2 (d, CHPh, J = 13.1 Hz), 118.0 (s, CHPh), 120.6 (s, CHAr),
3
1
1
1
1
1
1
22.7 (s, CHAr), 122.9 (s, CHAr), 123.3 (s, CH ), 123.9 (s, C ),
This study was financially supported by the Russian
Foundation for Basic Research (Project No. 08ꢀ03ꢀ00416ꢀa)
and the German Academic Exchange Service (Deutscher
Akademischer Austausch Dienst, DAAD, Germany).
Ar
Ar
24.7 (s, CH ), 124.9 (s, CH ), 125.1 (s, CH ), 125.9 (s, CH ),
Ar
Ar
Ar
Ar
26.0 (s, CH ), 127.5 (s, CH ), 127.7 (s, CH ), 128.4 (s, CH ),
Ar
Ar
Ar
Ar
28.6 (s, CHPh), 128.9 (s, C ), 129.5 (s, C ), 130.8 (s, C ),
Ar
Ar
Ar
2
33.7 (s, C ), 133.9 (s, C ), 146.8 (d, C , J = 16.7 Hz), 151.5
d, CAr, J = 3.1 Hz), 155.6 (s, CAr), 176.0 (s, C=O) (minor
epimer). H NMR (CDCl ), δ: 0.67 (s, 9 H); 1.39 (dq, 1 H,
Ar
Ar
Ph
2
(
1
References
3
J = 11.3 Hz); 1.58 (m, 2 H, J = 7.4 Hz, J = 7.3 Hz, J = 6.6 Hz);
1
2
.71 (dq, 1 H, J = 11.3 Hz); 2.53 (m, 1 H, J = 7.3 Hz, J = 6.5 Hz);
.90 (m, 2 H); 3.40 (m, 2 H); 6.70 (t, 1 H, J = 7.5 Hz); 7.00
1. J. M. Brown, in Comprehensive Asymmetric Catalysis, Eds
E. N. Jacobsen, A. Pfaltz, Y. Yamamoto, Springer, Berlin,
1999, 1, 121.
(
d, 2 H, J = 7.5 Hz); 7.10 (d, 2 H, J = 8.2 Hz); 7.15 (d, 1 H,
J = 7.3 Hz); 7.20 (dd, 1 H, J = 7.5 Hz, J = 7.1 Hz); 7.31 (ddd,
2. T. Ohkuma, M. Kitamura, R. Noyori, in Catalytic Asymmetꢀ
ric Synthesis, Ed. I. Ojima, Wiley—VCH, New York, 2000, 1.
3. M. J. Burk, Acc. Chem. Res., 2000, 33, 363.
4. H.ꢀU. Blaser, E. Schmidt, Asymmetric Catalysis on Industrial
Scale, Wiley—VCH, Weinheim, 2004.
2
=
H, J = 8.5 Hz, J = 7.0 Hz, J = 1.3 Hz); 7.38 (ddd, 2 H, J =
8.6 Hz, J = 7.1 Hz, J = 1.2 Hz); 7.41 (d, 2 H, J = 8.7 Hz); 7.61
(
d, 2 H, J = 8.3 Hz); 7.82 (d, 2 H, J = 8.8 Hz). IR (CHCl ),
3
–
1
+
ν/cm : 1742 (C=O). EI MS, m/z (Irel (%)): 575 [M] (5).
MALDI TOF/TOF MS, m/z (Irel (%)): 576 [M + H] (100).
+
5. M. Dieguez, A. Ruiz, C. Claver, J. Chem. Soc., Dalton Trans.,
2003, 2957.
Asymmetric hydrogenation of dimethyl itaconate (6) and methyl
2
ꢀ(Nꢀacetylamino)acrylate (7). A solution of [Rh(COD) ]BF4
6. J. Ansel, M. Wills, Chem. Soc. Rev., 2002, 31, 259.
7. A. Alexakis, C. Benhaim, Eur. J. Org. Chem., 2002, 19, 3221.
8. O. Molt, T. Shrader, Synthesis, 2002, 2633.
9. F. Fache, E. Schultz, M. L. Tommasino, M. Lemaire, Chem.
Rev., 2000, 100, 2159.
10. K. N. Gavrilov, O. G. Bondarev, A. I. Polosukhin, Usp.
Khim., 2004, 73, 726 [Russ. Chem. Rev. (Engl. Transl.), 2004,
73, 671].
2
(
0
0.001 g, 0.0025 mmol) and the corresponding ligand (0.0025 or
.005 mmol) in CH Cl (5 mL) was stirred for 40 min. Then the
2
2
corresponding substrate (0.5 mmol) was added, and the mixture
was placed in an autoclave. The catalytic apparatus was purged
with argon and then with hydrogen (three times), and then the
mixture was stirred at 25 °C for 20 h at a hydrogen pressure of
1
.3 atm. The reaction mixture was diluted with pentane (10 mL)
and filtered through a thin layer of silica gel. The solvents were
removed under reduced pressure (40 Torr), and the residue was
dried in vacuo (10 Torr). The conversions of substrates 6 and 7
and the optical yields of products 8 and 9 were determined by
GC and/or HPLC on chiral stationary phases.
11. M. T. Reetz, G. Mehler, A. Meiswinkel, T. Sell, Tetraheꢀ
dron Lett., 2002, 43, 7941.
12. J. M. Brunel, Chem. Rev., 2005, 105, 857.
13. M. Yan, Z.ꢀY. Zhou, A. S. C. Chan, Chem. Commun.,
2000, 115.
Asymmetric allylic alkylation of (E)ꢀ1,3ꢀdiphenylallyl acetate
14. L. Liang, A. S. C. Chan, Tetrahedron: Asymmetry, 2002,
13, 1393.
(
10) with dimethyl malonate. A solution of [Pd(All)Cl] (0.0037 g,
2
0
.01 mmol) and the corresponding ligand (0.02 or 0.04 mmol)
15. L. Liang, T. T.ꢀL. AuꢀYeung, A. S. C. Chan, Org. Lett.,
2002, 4, 3799.
(
or a solution of [Pt(All)Cl]4 (0.005 g, 0.005 mmol) and the
corresponding ligand (0.02 or 0.04 mmol)) in the corresponding
solvent (5 mL) was stirred for 40 min. (E)ꢀ1,3ꢀDiphenylallyl
acetate (10) (0.1 mL, 0.5 mmol) was added, and the reacꢀ
tion solution was stirred for 15 min. Then dimethyl malonate
16. L. Su, X. Li, W. L. Chan, X. Jia, A. S. C. Chan, Tetrahedron:
Asymmetry, 2003, 14, 1865.
17. L. Liang, M. Yan, Y.ꢀM. Li, A. S. C. Chan, Tetrahedron:
Asymmetry, 2004, 15, 2575.
(
0.10 mL, 0.87 mmol), BSA (0.22 mL, 0.87 mmol), and potassiꢀ
18. S. J. Sturla, S. L. Buchwald, J. Org. Chem., 2002, 67, 3398.
19. C. J. Cobley, R. D. J. Froese, J. Klosin, C. Qin, G. T. Whitekꢀ
er, K. A. Abboud, Organometallics, 2007, 26, 2986.
20. Y. Zou, Y. Yan, X. Zhang, Tetrahedron Lett., 2007, 48, 4781.
21. S. CserepiꢀSzucs, C. Huttner, L. Zsolnai, J. Bakos, J. Orgaꢀ
nomet. Chem., 1999, 586, 70.
um 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 pressure (40 Torr),
and the residue was dried in vacuo (10 Torr). The conversion of
substrate 10 and the optical yields of product 11 were deterꢀ
mined by HPLC on chiral stationary phases.
22. P. Kruger, B. Weberndorfer, H. Werner, Z. Anorg. Allg.
Chem., 2000, 626, 2228.
Asymmetric allylic amination of (E)ꢀ1,3ꢀdiphenylallyl acetate
(
0
(
10) with pyrrolidine. A solution of [Pd(All)Cl]2 (0.0037 g,
.01 mmol) and the corresponding ligand (0.02 or 0.04 mmol)
or a solution of [Pt(All)Cl]4 (0.005 g, 0.005 mmol) and the
23. V. Beghetto, A. Scrivanti, U. Matteoli, Catal. Commun., 2001,
2, 139.
24. 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.
25. K. N. Gavrilov, S. V. Zheglov, P. A. Vologzhanin, E. A.
Rastorguev, A. A. Shiryaev, M. G. Maksimova, 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].
corresponding ligand (0.02 or 0.04 mmol)) in the corresponding
solvent (5 mL) was stirred for 40 min. (E)ꢀ1,3ꢀDiphenylallyl
acetate (10) (0.1 mL, 0.5 mmol) was added, and the reaction
solution was stirred for 15 min. Then freshly distilled pyrrolidine
(
0.12 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 reduced pressure (40 Torr),
and the residue was dried in vacuo (10 Torr). The conversion of

440
Russ.Chem.Bull., Int.Ed., Vol. 59, No. 2, February, 2010
Gavrilov et al.
2
6. G. Buono, N. Toselli, D. Martin, in Phosphorus Ligands
in Asymmetric Catalysis, Ed. A. Börner, Wiley—VCH, Weinꢀ
heim, 2008, 2, 529.
7. M. T. Reetz, H. Oka, R. Goddard, Synthesis, 2003, 1809.
8. K. V. L. Crepy, T. Imamoto, Adv. Synth. Catal., 2003, 345, 79.
9. B. M. Trost, M. L. Crawley, Chem. Rev., 2003, 103, 2921.
0. T. Graening, H.ꢀG. Schmalz, Angew. Chem., Int. Ed., 2003,
39. T. Jerphagnon, J.ꢀL. Renaud, C. Bruneau, Tetrahedron:
Asymmetry, 2004, 15, 2101.
40. C. Najera, J. M. Sansano, Chem. Rev., 2007, 107, 4584.
41. A. J. Blacker, M. L. Clark, M. S. Loft, J. M. J. Williams,
Chem. Commun., 1999, 913.
42. A. J. Blacker, M. L. Clark, M. S. Loft, M. F. Mahon, M. E.
Humphries, J. M. J. Williams, Chem. Eur. J., 2000, 6, 353.
43. H. Hocke, Y. Uozumi, Tetrahedron, 2003, 59, 619.
44. T. V. RajanBabu, T. A. Ayers, G. A. Halliday, K. K. You,
J. C. Calabrese, J. Org. Chem., 1997, 62, 6012.
45. P. R. Auburn, P. B. McKenzie, B. Bosnich, J. Am. Chem.
Soc., 1985, 107, 2033.
2
2
2
3
42, 2580.
3
3
1. Z. Lu, S. Ma, Angew. Chem., Int. Ed., 2008, 47, 258.
2. 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.,
2
004, 2214.
46. J. Lukas, Inorg. Synth., 1974, 15, 75.
3
3
3. S. Iriuchijima, Synthesis, 1978, 684.
4. J. M. Brunel, T. Constantieux, G. Buono, J. Org. Chem.,
47. M. T. Reetz, J.ꢀAn Ma, R. Goddard, Angew. Chem., Int. Ed.,
2005, 44, 412.
1
999, 64, 8940.
48. K. N. Gavrilov, S. E. Lyubimov, S. V. Zheglov, E. B.
Benetsky, V. A. Davankov, J. Mol. Catal. A, 2005, 231, 255.
3
5. H. Arzoumanian, G. Buono, M. Choukrad, J.ꢀF. Petrigꢀ
nani, Organometallics, 1988, 7, 59.
3
3
6. M. Kimura, Y. Uozumi, J. Org. Chem., 2007, 72, 707.
7. C. J. Ngono, T. Constantieux, G. Buono, Eur. J. Org. Chem.,
2
006, 1499.
3
8. K. N. Gavrilov, E. B. Benetsky, T. B. Grishina, S. V. Zheꢀ
glov, E. A. Rastorguev, P. V. Petrovskii, F. Z. Macaev, V. A.
Davankov, Tetrahedron: Asymmetry, 2007, 18, 2557.
Received May 13, 2009;
in revised form September 8, 2009