Phosphorylated (S)-tert-leucinol isophthalic diamide as a ligand for Pd-catalyzed asymmetric allylic substitution

Article abstract of DOI:10.1007/s11172-014-0791-4

O-Phosphorylation of N,N′-(isophthaloyl)di-(S)-tert-leucinol with (5S)-2-chloro-3-phenyl-1,3-diaza-2-phosphabicyclo[3.3.0]octane afforded bidentate phosphite-type ligand. This ligand provided 93% ee in Pd-catalyzed enantioselective allylation of (E)-1,3-d

Full text of DOI:10.1007/s11172-014-0791-4

Russian Chemical Bulletin, International Edition, Vol. 63, No. 12, pp. 2635—2640, December, 2014
2635
Phosphorylated (S)ꢀtertꢀleucinol isophthalic diamide as a ligand
for Pdꢀcatalyzed asymmetric allylic substitution
K. N. Gavrilov,a S. V. Zheglov, N. N. Groshkin, V. K. Gavrilov, M. G. Maksimova,
a
a
a
a
b
b
A. N. Volov, and I. A. Zamilatskov
aS. A. Esenin Ryazan State University,
4
6 ul. Svobody, 390000 Ryazan, Russian Federation.
Fax: +7 (491 2) 28 1435. Eꢀmail: k.gavrilov@rsu.edu.ru
A. N. Frumkin Institute of Physical Chemistry and Electrochemistry, Russian Academy of Sciences,
b
3
1 Leninsky prosp., 119071 Moscow, Russian Federation.
Fax: +7 (495) 952 0449. Eꢀmail: alex123.87@mail.ru
OꢀPhosphorylation of N,N´ꢀ(isophthaloyl)diꢀ(S)ꢀtertꢀleucinol with (5S)ꢀ2ꢀchloroꢀ3ꢀ
phenylꢀ1,3ꢀdiazaꢀ2ꢀphosphabicyclo[3.3.0]octane afforded bidentate phosphiteꢀtype ligand. This
ligand provided 93% ee in Pdꢀcatalyzed enantioselective allylation of (E)ꢀ1,3ꢀdiphenylallyl
acetate, and 55% ee in alkylation of cinnamyl acetate with ethyl 2ꢀoxocyclohexaneꢀ1ꢀcarbꢀ
oxylate.
Key words: amino alcohols, diamines, diamidophosphites, palladium catalysts, asymmetric
allylation.
Activity and stereoselectivity of metal complex cataꢀ
lysts are mainly determined by the success in design and
synthesis of the corresponding chiral ligands. Phosphoꢀ
rusꢀcontaining chiral ligands repeatedly used in various
1
—7
asymmetric transformations are of special interest.
The
metal complexes comprising the vast majority of chiral
phosphorus ligands have proven to afford the excellent
enantiomeric control only in certain chemical transforꢀ
mations. Only few ligands have a general scope (so called
privileged ligands); moreover, a high cost of these ligands
limited their wide applications. Consequently, the design
of novel effective phosphorusꢀcontaining chiral inductors
readily accessible from enantiomerically pure building
8
—12
blocks is still urgent.
starting material for the introduction of the phosphorus
chiral centers. Thus, phosphinite derivatives of diamides
One of the promising strategies to achieve this goal is
the synthesis of ligands combining the advantages of orꢀ
ganic and phosphorus chiral inductors.1
3—15
The synthetꢀ
of oxalic acid with available chiral amino alcohols L have
B
been found to be effective in Ruꢀcatalyzed asymmetric
ic approaches towards these ligands may involve either
introduction of organocatalytic functional groups into the
molecules of chiral phosphines or direct phosphorylation
of different organocatalysts. For instance, thiourea P,Pꢀbiꢀ
dentate ligand LA obtained via reaction of ferrocenyl
aminobisphosphine with substituted phenyl isothiocyanꢀ
ate shows excellent enantioselectivity in Rhꢀcatalyzed
hydrogenation of nitroalkenes.16
2
1—23
transfer hydrogenation of aromatic ketones.
Howevꢀ
er, the significant disadvantage of these compounds is their
2
1
high sensitivity to oxidation and hydrolysis.
Amides derived from enantiomerically pure amino
alcohols (these compounds are efficient organocatalysts
for asymmetric reduction of ketimines with trichlorosilane
and ketones with borane1
7—20
) can be regarded as suitable
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2635—2640, December, 2014.
066ꢀ5285/14/6312ꢀ2635 © 2014 Springer Science+Business Media, Inc.
1

2636
Russ.Chem.Bull., Int.Ed., Vol. 63, No. 12, December, 2014
Gavrilov et al.
In this regard, inexpensive phosphite ligands stable to
oxidation and exhibiting pronounced acidity are more
promising. Accessibility of phosphite ligands via condenꢀ
ing of its steric and electronic properties.35,36 A stereogenꢀ
ic donor phosphorus atom is directly bonded to a central
chelating atom (ion) and is in closest proximity to the
chelated substrate thus promoting the effective asymmetꢀ
sation reactions including parallel and solidꢀphase synꢀ
theses1
1,24—29
are also of note. At the same time, the known
ric induction on the key stage of the catalytic cycle.
2,12,37
asymmetric phosphite inductors derived from amides of
carboxylic acids with chiral amino alcohols are limited
only to compounds LC.
The enantioselectivity of a novel diamidophosphite 1
was examined on the examples of the asymmetric
Pdꢀcatalyzed allylic substitutions. On the one hand, these
reactions are the reliable models to evaluate the efficiency
of the novel chiral ligands. On the other hand, the Pdꢀcatꢀ
alyzed allylic substitution is tolerated to different funcꢀ
tional groups in allylic substrates and is widely used for the
asymmetric synthesis of valuable organic and natural comꢀ
30—32
4
,37—40
pounds.
For example, the products of alkylation
with dimethyl malonate readily underwent transformaꢀ
tions to give the esters and amides of chiral unsaturated
carboxylic acids under mild conditions and in the absence
4
1
of a C*ꢀchiral center.
Results and Discussion
Isophthaloyl dichloride 2 smoothly reacts with (S)ꢀtertꢀ
leucinol (3) in CH Cl in the presence of a catalytic
2
2
amount of DMAP and a triethylamine excess to give isoꢀ
phthaloyl diamido diol 4 (Scheme 1). Further direct phosꢀ
In the present work, we describe the synthesis and apꢀ
plication in asymmetric catalysis of P*,P*ꢀbidentate diꢀ
amidophosphite 1 bearing 1,3,2ꢀdiazaphospholidine cycles
and fragments of diamide of isophthalic acid with (S)ꢀtertꢀ
leucinol.
Scheme 1
It should be noted that these diamides provide good
results in asymmetric Tiꢀ and Znꢀcatalyzed conjugate
3
3,34
addition of terminal alkynes.
Moreover, P*ꢀchiral
1
,3,2ꢀdiazaphospholidines are very interesting family of
chirogenic diamidophosphite ligands. In particular, these
compounds owing to the finely balanced electronic propꢀ
erties are able to act as both good  acceptors (due to the
availability of the low energy *PN orbitals) and good

donors. Phosphorus atom of the phospholidine increasꢀ
es the stability of the ligand towards oxidation and hydrolꢀ
ysis; while, the possibility to widely vary the substituents
at the phosphorus and/or nitrogen atoms allows the turnꢀ

Phosphorylated isophthalic diamide
Russ.Chem.Bull., Int.Ed., Vol. 63, No. 12, December, 2014 2637
phorylation of compound 4 in toluene affords P*,P*ꢀbiꢀ
dentate diamidophosphite 1. Note that phosphorylating
4
2
reagent 5 is readily available in good yield from (S)ꢀglutꢀ
4
3,44
amic acid anilide.
Ligand 1 is enantiomerically pure. The presence of the
31
sharp singlet signal at  125.7 in the P NMR spectrum
P
Fig. 1. Schematic representation of the fragment of the structure
of ligand 1 (X is an exocyclic substituent).
(
CDCl ) of ligand 1 indicates the (R)ꢀconfiguration of the
3
P*ꢀchiral centers. The large spinꢀspin coupling constant
value J
2
13
= 37.6 Hz in the C NMR spectrum reveals
C(8),P
that the exocyclic substituent at the P atom occupies
a pseudoꢀequatorial position and is anti with respect to
The highest conversions were achieved in CH Cl . In
all cases, (S) enantiomer of product 8 predominates.
The use of pyrrolidine as an N nucleophile produces
0% ee with enantiomer (R)ꢀ9 being the major product
see Table 3). The highest asymmetric induction was obꢀ
2
2
the —(CH ) — moiety of the pyrrolidine cycle of phosꢀ
2
3
phabicyclo[3.3.0]octane core and, consequently, the lone
electron pair at the P atom and the C(8) atom are in the
9
(
4
2—47
syn conformation (Fig. 1).
served in CH Cl at a molar ratio of L/Pd = 2. In the vast
2
2
Diamidophosphite 1 can be easily purified by flash
column chromatography; it is relatively stable in air and
can be stored for a long time under dry conditions. Takꢀ
ing into account the availability of the starting comꢀ
pounds, ligand 1 can be synthesized in gramꢀscale
amounts. First, we evaluated the catalytic performance of
diamidophosphite 1 in three model reactions of asymꢀ
metric Pdꢀcatalyzed allylation using (E)ꢀ1,3ꢀdiphenylꢀ
allyl acetate (6). As a precatalyst, [Pd(allyl)Cl]2 was
applied (Scheme 2, Tables 1—3). Allylic sulfonylation of
compound 6 with sodium pꢀtoluenesulfinate (S nucleoꢀ
phile) results in sulfone (R)ꢀ7 with good enantioselectivity
majority of cases, the conversion of the starting substrate 6
was quantitative.
Enantioselective catalytic synthesis of compounds
bearing the quaternary asymmetric atoms is a relatively
complex task. One of the approaches to access these type
of compounds is the Pdꢀcatalyzed allylic substitution genꢀ
erating the C*ꢀchiral center at the carbon atom of the
nucleophile. Stereoselectivity of such allylation is difficult
to control, since the nucleophile approaches the allylic
3
fragment of a  ꢀallylpalladium(II) intermediate from the
Table 1. Pdꢀcatalyzed sulfonylation of substrate 6 with
sodium pꢀtoluenesulfinatea
(
(
up to 86% ee); the optimum L/Pd molar ratio is 1
see Table 1).
Entry
L/Pd
Yield (%)
ee (%)b
Scheme 2
1
2
1
2
71
55
86 (R)
78 (R)
a
All reactions were carried out in THF at 20 C, 48 h,
2
mol.% [Pd(allyl)Cl]2.
Enantiomeric excesses of product 7 were measured by
b
i
HPLC (Daicel Chiralcel ODꢀH, C H /Pr OH = 4 : 1,
0
6
14
.5 mL min– , 254 nm, t(R) = 16.3 min, t(S) =
1
=
18.5 min).
Table 2. Pdꢀcatalyzed alkylation of substrate 6 with dimeꢀ
thyl malonatea
Entry L/Pd
Solvent
Conversion (%)
ee (%)b
1
2
3
4
1
2
1
2
THF
THF
160
141
168
100
93 (S)
91 (S)
88 (S)
91 (S)
i. pꢀTolSO Na, Cat.; ii. CH (CO Me) , BSA, Cat.;
2
2
2
2
iii. (CH ) NH, Cat.
2
4
CH Cl2
2
CH Cl2
2
Cat is [Pd(allyl)Cl] —1 (1 : 2 molar ratio), BSA is N,Oꢀbis(trimethꢀ
2
ylsilyl)acetamide.
a
All reactions were carried out at 20 C, 48 h, 2 mol.%
[
Pd(allyl)Cl]2.
In allylic alkylation of substrate 6 with dimethyl malꢀ
onate (C nucleophile), P*,P*ꢀbidentate ligand 1 provides
the high enantioselectivity (ee 88—93%) regardless of both
the solvent nature and the L/Rh molar ratio (Table 2).
b
Conversion of substrate 6 and enantiomeric excesses of
product 8 were determined by HPLC (Daicel Chiralcel
OD—H, C H /Pr OH = 99 : 1, 0.3 mL min , 254 nm,
t(R) = 28.0 min, t(S) = 29.3 min).
i
–1
6
14

2638
Russ.Chem.Bull., Int.Ed., Vol. 63, No. 12, December, 2014
Gavrilov et al.
Table 3. Pdꢀcatalyzed amination of substrate 6 with pyrroꢀ
lidine
The L/Pd molar ratio does not virtually affect the conꢀ
version and enantioselectivity of the reaction carried out
in CH Cl ; however, in toluene the increase in the L/Pd
molar ratio to 2 results in an insignificant increase in the
conversion and noticeable decrease in the asymmetric inꢀ
duction. In all cases, (S)ꢀenantiomer of product 12 predoꢀ
minates.
In summary, in the present work we described the synꢀ
thesis of ligand 1, the first representative of P,Pꢀbidentate
phosphite ligands bearing the fragment of amide derived
from chiral amino alcohol. Ligand 1 provides 93% ee in
asymmetric Pdꢀcatalyzed allylation of sodium pꢀtolueneꢀ
sulfinate with (E)ꢀ1,3ꢀdiphenylallyl acetate (6) and 55%
ee in alkylation of cinnamyl acetate (10) with ethyl
a
2
2
Entry L/Pd
Solvent
Conversion (%) ee (%)b
1
2
3
4
1
2
1
2
THF
THF
100
190
100
100
84 (R)
71 (R)
81 (R)
90 (R)
CH Cl2
2
CH Cl2
2
a
All reactions were carried out at 20 C, 48 h, 2 mol.%
[
b
Pd(allyl)Cl]2.
Conversion of substrate 6 and enantiomeric excesses of
product 9 were determined by HPLC (Daicel Chiralcel
i
–1
OD—H, C H /Pr OH/HNEt = 200 : 1 : 0.1, 0.9 mL min
,
6
14
2
2
54 nm, t(R) = 5.0 min, t(S) = 6.1 min).
2ꢀoxocyclohexanecarboxylate (11). Thus, ligand 1 can be
regarded as a promising chiral inductor.
side opposite to a central chelating atom and coordinated
4
2,48—50
to it chiral ligand.
asymmetric alkylation of cinnamyl acetate (10) with ethyl
ꢀoxocyclohexanecarboxylate (11), is given in Scheme 3.
When diamidophosphite 1 was used as a chiral inductor,
The example of this reaction,
Experimental
2
31
P, H, and 13C NMR spectra were recorded on Bruker
1
Avance 400 (161.98, 400.13, and 100.61 MHz) and Bruker
Avance III 600 (242.94, 600.13, and 150.9 MHz) instruments,
the chemical shifts are given in the  scale relative to 85% H PO
5
5% ee was achieved (Table 4).
3
4
1
13
Scheme 3
in D2O and Me4Si, respectively. The signals in H and C NMR
spectra were attributed using COSY, DEPT, and HSQC NMR
4
2—44
techniques taking into account the published data.
Matrixꢀ
assisted laser desorption/ionization mass spectrometry (MALDI
TOF/TOF) was performed with a Bruker Daltonics Ultraflex
instrument. Enantiomeric excesses of the products were meaꢀ
sured with a Staier HPLC system. Elemental analyses were carꢀ
ried out with a Carlo Erba EA1108 CHNSꢀO analyzer.
All reactions were carried out under dry argon in anhydrous
1
3
solvents. N ,N ꢀBis((S)ꢀ1ꢀhydroxyꢀ3,3ꢀdimethylbutꢀ2ꢀyl)isoꢀ
3
3
51
phthalamide (4) , (E)ꢀ1,3ꢀdiphenylallyl acetate (6), and
[
Pd(allyl)Cl]25 were synthesized by the known procedures.
1
Asymmetric allylation of substrate 6 with sodium pꢀtoluenesulfiꢀ
nate, dimethyl malonate, and pyrrolidine, alkylation of subꢀ
strate 10 with nucleophile 11, as well as the measurements of
conversion of substrates 6 and 10 and enantiomeric excesses of
products 7, 8, 9, and 12 were performed following the
described procedures.
Cat is [Pd(allyl)Cl] —1 (1 : 2 molar ratio).
2
4
2
52
49
50
Isophthaloyl dichloride (2), (S)ꢀtertꢀleucinol (3), 4ꢀdiꢀ
methylaminopyridine (DMAP), sodium pꢀtoluenesulfinate, diꢀ
methyl malonate, bis(trimethylsilyl)acetamide (BSA), pyrroliꢀ
dine, cinnamyl acetate (10), and ethyl 2ꢀoxocyclohexanecarbꢀ
oxylate (11) are commercially available from Fluka and Aldrich.
Table 4. Pdꢀcatalyzed alkylation of substrate 10 with ethyl
2
ꢀoxocyclohexanecarboxylatea
Entry L/Pd
Solvent
Conversion (%)
ee (%)b
1
3
N ,N ꢀBis((S)ꢀ1ꢀhydroxyꢀ3,3ꢀdimethylbutꢀ2ꢀyl)isophthalꢀ
amide (4). To a vigorously stirred solution of (S)ꢀtertꢀleucinol (3)
1
2
3
4
1
2
1
2
Toluene
Toluene
187
199
100
100
55 (S)
34 (S)
42 (S)
44 (S)
(
(
1.17 g, 10 mmol), Et N (4.17 mL, 30, mmol), and DMAP
3
0.12 g, 1 mmol) in CH Cl (20 mL), a solution of isophthaloyl
CH Cl2
2
2
2
dichloride (2) (1.02 g, 5 mmol) in CH Cl (10 mL) was added
CH Cl2
2
2
2
dropwise over a period of 30 min at 0 C. Then the reaction
mixture was stirred at 20 C for 24 h, diluted with CH Cl
a
All reactions were carried out at 20 C, 48 h, 2 mol.%
2
2
[
b
Pd(allyl)Cl]2.
(10 mL), washed with 1 M HCl (2×10 mL), saturated aqueous
Conversion of substrate 10 and enantiomeric excesses of
NaHCO (3×10 mL), and brine (3×10 mL). The organic layer
3
product 12 were determined by HPLC (Kromasil 5ꢀCelluꢀ
was dried with MgSO , filtered, and the solvent was removed
in vacuo (40 Torr). The obtained yellow solid was washed with
hexane (2×10 mL) to give target product 4 in the yield of 1.35 g
4
i
–1
Coat, C H /Pr OH = 95 : 5, 0.4 mL min , 254 nm,
6
14
t(R) = 14.3 min, t(S) = 16.4 min).

Phosphorylated isophthalic diamide
Russ.Chem.Bull., Int.Ed., Vol. 63, No. 12, December, 2014 2639
(
74%), white powder, m.p. 123—124 C. Found (%): C, 66.17;
40 min and (E)ꢀ1,3ꢀdiphenylallyl acetate (0.1 mL, 0.5 mmol)
was added. After 15 min stirring, dimethyl malonate (0.1 mL,
0.87 mmol), BSA (0.22 mL, 0.87 mmol), and AcOK (2 mg) were
added. The reaction mixture was stirred for 48 h, diluted with
hexane (5 mL), and filtered through a Celite pad. The solvents
were removed in vacuo (40 Torr) and residue was dried in vacuo
(10 Torr). Conversion of substrate 6 and enantiomeric excesses
of product 8 were measured by HPLC using chiral stationꢀ
ary phase.
H, 8.96; N, 7.50. C20H32N O . Calculated (%): C, 65.91;
H, 8.85; N, 7.69. 13C NMR (DMSOꢀd ), : 27.4 (s, CH ); 34.4
(
(
(
(
2
4
6
3
s, C); 59.9 (s, CHN); 60.6 (s, CH O); 127.0 (s, C(2´)); 128.1
2
s, C(5´)), 130.0 (s, C(4´), C(6´)); 135.7 (s, C(1´), C(3´)); 167.1
1
s, C=O). H NMR (DMSOꢀd ), : 0.91 (s, 18 H, CH ); 3.44—3.53
6
3
m, 2 H); 3.61—3.69 (m, 2 H); 3.85—3.94 (m, 2 H); 4.45 (br.s,
3
2
H, OH); 7.52 (t, 1 H, C(5´)H, J = 7.6 Hz); 7.96 (dd, 2 H,
3
4
C(4´)H, C(6´)H, J = 7.6 Hz, J = 1.6 Hz); 8.03 (d, 2 H, NH,
3
J = 9.2 Hz); 8.28 (br.s, 1 H, C(2´)H).
Asymmetric amination of (E)ꢀ1,3ꢀdiphenylallyl acetate (6) with
1
3
N ,N ꢀBis[(S)ꢀ1ꢀ((2R,5S)ꢀ3ꢀphenylꢀ1,3ꢀdiazaꢀ2ꢀphosphaꢀ
pyrrolidine. A solution of [Pd(allyl)Cl] (0.0037 g, 0.01 mmol)
2
bicyclo[3.3.0]octꢀ2ꢀyloxy)ꢀ3,3ꢀdimethylbutꢀ2ꢀyl]isophthalamide
and ligand 1 (0.0155 g, 0.02 mmol or 0.0309 g, 0.04 mmol) in the
corresponding solvent (5 mL) was stirred for 40 min and
(E)ꢀ1,3ꢀdiphenylallyl acetate (0.1 mL, 0.5 mmol) was added.
After 15 min stirring, 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 a Celite pad.
The solvents were removed in vacuo (40 Torr), the residue was
dried in vacuo (10 Torr). Conversion of substrate 6 and enantioꢀ
meric excesses for product 9 were measured by HPLC using
chiral stationary phase.
(
1). To a vigorously stirred solution of phosphorylating reagent 5
(
0.48 g, 2 mmol) and Et N (0.56 mL, 4 mmol) in toluene (20 mL),
3
compound 4 (0.36 g, 1 mmol) was added in one portion at 20 C.
The mixture was stirred for 24 h, precipitated Et N•HCl was
3
filtered off, and the filtrate was concentrated in vacuo (40 Torr).
The flash alumina chromatography (elution with toluene) afꢀ
forded the target product 1 in the yield of 0.67 g (86%), white
powder, m.p. 88—89 C. Found (%): C, 65.49; H, 7.61; N, 10.75.
C H N O P . Calculated (%): C, 65.27; H, 7.56; N, 10.87.
4
2
58
6
4 2
1
3
3
C NMR (CDCl ), : 26.1 (d, C(7), JC,P = 3.8 Hz); 27.4
s, CH ); 32.2 (s, C(6)); 35.0 (s, C); 48.7 (d, C(8), J = 37.6 Hz);
Asymmetric alkylation of cinnamyl acetate 10 with ethyl 2ꢀ
oxocyclohexanecarboxylate (11). A solution of [Pd(allyl)Cl]2
3
2
(
3
C,P
2
5
6
1
4.8 (d, C(4), J
= 7.2 Hz); 56.7 (s, CHN); 62.1 (s, CH O);
(0.0037 g 0.01 mmol) and ligand 1 (0.0155 g, 0.02 mmol or
0.0309 g, 0.04 mmol) in the corresponding solvent (5 mL) was
stirred for 40 min and cinnamyl acetate (0.08 mL, 0.5 mmol) was
added. After 15 min stirring, ethyl 2ꢀoxocyclohexanecarboxylꢀ
ate (0.12 mL, 0.75 mmol), BSA (0.5 mL, 2 mmol) and Zn(AcO)2
(0.01 g) were added. The reaction mixture was stirred for 48 h,
diluted with hexane (5 mL), and filtered through a Celite pad.
The volatiles were removed in vacuo (40 Torr) and the residue
was dried in vacuo (10 Torr). Conversion of substrate 10 and
enantiomeric excesses for product 12 were measured by HPLC
using chiral stationary phase.
C,P
2
3.6 (d, C(5), J = 8.4 Hz); 114.8 (d, oꢀCHPh, 3J = 12.1 Hz);
2
C,P
C,P
19.2 (s, pꢀCHPh); 125.7 (s, C(2´)); 128.7 (s, C(5´)); 129.1
(
1
s, mꢀCHPh); 129.6 (s, C(4´), C(6´)); 135.5 (s, C(1´), C(3´));
2
1
45.3 (d, CPh, J = 15.6); 166.6 (s, C=O). H NMR (CDCl ),
C
,
P
3

: 1.05 (s, 18 H, CH ); 1.59—1.66 (m, 2 H, C(6)H); 1.68—1.75
3
(
(
m, 2 H, C(7)H); 1.76—1.83 (m, 2 H, C(7)H); 2.02—2.09
m, 2 H, C(6)H); 2.94—3.0 (m, 2 H, C(8)H); 3.17—3.22 (m, 2 H,
C(4)H); 3.42—3.48 (m, 2 H, C(8)H); 3.70—3.78 (m, 4 H, C(4)H,
CH O); 4.02—4.08 (m, 2 H, CH O); 4.09—4.14 (m, 2 H, CHN);
2
2
3
4
6
3
.16—4.22 (m, 2 H, C(5)H); 6.72 (d, 2 H, NH, J = 9.7 Hz);
.76 (t, 2 H, (pꢀCPh)H, J = 7.5 Hz); 6.97 (br.d, 4 H, (oꢀCPh)H,
J = 7.8 Hz); 7.13 (br.t, 4 H, (mꢀC )H, J = 7.9 Hz); 7.46
t, 1 H, C(5´)H, J = 7.7 Hz); 7.83 (dd, 2 H, C(4´)H, C(6´)H,
J = 7.7 Hz, 4J = 1.6 Hz); 8.13 (br.s, 1 H, C(2´)H). MS
MALDI TOF/TOF), m/z (I (%)): 773 [M + H] (100), 715
M – Bu ] (82).
3
3
This work was financially supported by the Russian
Foundation for Basic Research (Project No. 14ꢀ03ꢀ00396ꢀa)
and Ministry of Education and Science of Russian Federꢀ
ation (Grant 2014/378).
Ph
3
(
3
+
(
[
rel
t +
Asymmetric sulfonylation of (E)ꢀ1,3ꢀdiphenylallyl acetate (6)
References
with sodium pꢀtoluenesulfinate. A solution of [Pd(allyl)Cl]2
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(
0
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Received February 17, 2014;
in revised form May 15, 2014