Pd-Catalyzed asymmetric transformations involving P*-mono- and P*,N-bidentate diamidophosphites derived from (2S,3S)-N 2,3-dimethyl-N 1-phenylpentane-1,2-diamine

Article abstract of DOI:10.1007/s11172-012-0267-3

The synthesis of new P*-mono- and P*,N-bidentate diamidophosphites, containing 1,3,2-diazaphospholidine rings formed starting from (2S,3S)-N ²,3-dimethyl-N ¹-phenylpentane-1,2-diamine, is described. Comparison of their efficiency in

Full text of DOI:10.1007/s11172-012-0267-3

Russian Chemical Bulletin, International Edition, Vol. 61, No. 10, pp. 1925—1932, October, 2012
1925
PdꢀCatalyzed asymmetric transformations involving
P*ꢀmonoꢀ and P*,Nꢀbidentate diamidophosphites derived from
(2S,3S)ꢀN2,3ꢀdimethylꢀN1ꢀphenylpentaneꢀ1,2ꢀdiamine
K. N. Gavrilov,a I. V. Chuchelkin,a S. V. Zheglov,a A. A. Shiryaev,a O. V. Potapova,a I. M. Novikov,a
E. A. Rastorguev,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) 28 1435. Eꢀmail: k.gavrilov@rsu.edu.ru
bA. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences,
28 ul. Vavilova, 119991 Moscow, Russian Federation.
Fax: +7 (499) 135 6471. Eꢀmail: hagehoge@mail.ru
The synthesis of new P*ꢀmonoꢀ and P*,Nꢀbidentate diamidophosphites, containing
1,3,2ꢀdiazaphospholidine rings formed starting from (2S,3S)ꢀN2,3ꢀdimethylꢀN1ꢀphenylꢀ
pentaneꢀ1,2ꢀdiamine, is described. Comparison of their efficiency in the Pdꢀcatalyzed enantioꢀ
selective allylation with (E)ꢀ1,3ꢀdiphenylallyl acetate showed that up to 97% ee was reached in
the reaction involving dimethyl malonate as a Cꢀnucleophile. The Pdꢀcatalyzed desymmetriꢀ
zation of N,N´ꢀditosylꢀmesoꢀcyclopentꢀ4ꢀeneꢀ1,3ꢀdiol biscarbamate gave up to 61% ee.
Key words: diamidophosphites, 1,3,2ꢀdiazaphospholidines, palladium catalysts, asymmetꢀ
ric allylation, desymmetrization.
Preparation of enantiopure or, in general case, enantioꢀ
enriched organic and organoelement compounds is one of
the main directions in development of modern synthetic
chemistry. This is due to the practical importance of such
substances as main components of pharmaceutical drugs,
chemical agent for protection of agricultural and natural
plantations, perfumery compositions, food additives and
flavors. The most efficient approach to the preparation of
enantioenriched compounds consists in the asymmetric
synthesis involving the use of catalytic amounts of inducꢀ
tor of chirality. Such an approach was successfully realꢀ
ized, in particular, in the enantioselective metal complex
catalysis.1—6 Activity and stereoselectivity of metal comꢀ
plex catalysts are determined significantly by a proper stratꢀ
egy of design and synthesis of the corresponding chiral
ligands, first of all, phosphorusꢀcontaining ones, thouꢀ
sands of representatives of which were used in various
asymmetric transformations.1,2,4,7—9
ration of inexpensive ligands based on available chiral synꢀ
thons is still a challenging problem.10—14 The ligands of
the phosphite nature are of considerable interest, since
they are favorably distinguished by stability to oxidation,
pronounced ꢀacidity, and are inexpensive. Note also that
they can be easily obtained by simple condensation proꢀ
cesses, including those involving parallel and solidꢀphase
synthetic procedures.13,15—20
An attractive group are diamidophosphite ligands, in
which the tricoordinated phosphorus atom is included into
the phospholidine ring LA—E
.
Nonetheless, the overwhelming majority of such ligꢀ
ands can, being a part of the corresponding metal comꢀ
plex, catalyze with different enantioselectivity only a cerꢀ
tain type of chemical transformations or one certain reacꢀ
tion. Existing versatile (the soꢀcalled "privileged") ligands
are very scarce, whereas the high cost considerably limits
their wide practical application. In this connection, deꢀ
velopment of simple and efficient methods for the prepaꢀ
They exhibit properties of both good ꢀacceptors (due
to the availability of the lowꢀlying *PNꢀorbitals) and good
† Deceased.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1910—1917, October, 2012.
1066ꢀ5285/12/6110ꢀ1925 © 2012 Springer Science+Business Media, Inc.

1926
Russ.Chem.Bull., Int.Ed., Vol. 61, No. 10, October, 2012
Gavrilov et al.
ꢀdonors. Incorporation of a phosphorus atom into the
phospholidine ring increases stability of the ligand to oxiꢀ
dation and hydrolysis, whereas a rich possibilities to vary
substituents at the phosphorus and/or nitrogen atoms alꢀ
lows one to control its steric and electronic characterisꢀ
tics.21,22 The presence of the asymmetric donor phosphoꢀ
rus atom considerably assists in the transformation of
chirality in the key step of the catalytic cycle.2,14 Thus,
Results and Discussion
The starting enantiopure diamine 3 was obtained by
the condensation of NꢀBocꢀLꢀisoleucine 4 and aniline with
subsequent hydride reduction of the formed amide 5
(Scheme 1).42
New P*ꢀchiral diamidophosphites 1 and 2 were synꢀ
thesized by means of oneꢀstep phosphorylation of adaꢀ
mantanol 6 or iminoalcohol 7 with the agent 8 (obtained
by us for the first time) in toluene (Scheme 2).
P*ꢀmonoꢀ and P*,Nꢀbidentate diamidophosphites LA—D
,
in which the phospholidine ring is a part of 2ꢀphosꢀ
phabicyclo[3.3.0]octane framework, are successfully
used in the asymmetric Pdꢀ and Irꢀcatalyzed allylation,
Rhꢀcatalyzed addition, and Rhꢀcatalyzed hydration
reactions.23—31 At the same time, monocyclic diamidoꢀ
phosphites LE and LF have proved unsuccessful stereoꢀ
selectors: their involvement into the Pdꢀ and Irꢀcatalyzed
allylation of dimethyl malonate led to virtually racemic
products.32,33
Note that the phosphorylating agent 8 was formed easꢀ
ily and in good yield by the reaction of diamine 3 with
PCl3 in benzene in the presence of Et3N as an acceptor of
hydrogen chloride. The agent 8 is stable on storage under
dry atmosphere, can be easily purified by vacuum distillaꢀ
tion and accumulated on a multigram scale. The presence
of the only sharp singlet signal at  158.2 in the 31P NMR
spectrum of compound 8 (in CDCl3) indicates that either
it is individual stereo isomer or exists as rapidly interconꢀ
versible epimers at the phosphorus stereocenter.43
Diamidophosphites 1 and 2 were isolated by flashꢀ
chromatography, they are well soluble in most organic
solvents, are stable enough in air and on prolonged storage
under dry atmosphere. Compounds 1 and 2 are mixtures
of epimers at the P*ꢀstereocenter in the ratio ~1 : 2. This
follows from the presence of two singlet signals with the
corresponding intensities in the 31P NMR spectra of their
solutions in CDCl3 (Table 1). The steric requirements of 1
and 2 are virtually identical, which is confirmed by close
values of their Tolmann cone angles () (see Table 1)
calculated using the AM1 semiempirical quantum chemiꢀ
cal method with full optimization of geometric paraꢀ
meters.44,45
The reaction of P*,Nꢀbidentate ligand 2 with
[Pd(allyl)Cl]2 (in the presence of AgBF4) leads to the forꢀ
mation of cationic metal chelate 9 with cisꢀorientation of
the phosphorus and the nitrogen atoms (Scheme 3). The
31P NMR spectrum of its solution in CDCl3 exhibits broad
singlets at P 122.5 and 121.2 with the intensities of 44 and
24%, respectively, related to the exoꢀ and endoꢀisomers of
one of the epimers of complex 9, as well as a sharp singlet
signal at  115.1 and the intensity of 32% related to the
another epimer of 9. The presence in the latter case of
a sharp symmetric singlet indicates either a rapid interꢀ
Thus, the synthesis of new efficient monocyclic diꢀ
amidophosphite ligands of phospholidine series having
stereogenic phosphorus atoms is still an actual problem.
In the present work, we report on the synthesis and appliꢀ
cation in enantioselective catalysis of their representatives,
viz., P*ꢀmonoꢀ and P*,Nꢀbidentate compounds derived
from (2S,3S)ꢀN2,3ꢀdimethylꢀN1ꢀphenylpentaneꢀ1,2ꢀdiꢀ
amine (1 and 2, respectively). We have chosen Pdꢀcataꢀ
lyzed asymmetric allylation and desymmetrization reacꢀ
tions as the catalytic processes for their examination. From
the one hand, such transformations are effective methods
for the evaluation of efficiency of new chiral ligands. From
the other hand, being indifferent to various functional
groups in the structure of the substrate and operating a vast
range of Cꢀ, Nꢀ, Oꢀ, Sꢀ, and Pꢀnucleophiles, these reacꢀ
tions are widely used in the key steps of asymmetric synꢀ
theses of important organic and naturally occurring comꢀ
pounds.34—38 In particular, the allylation products of diꢀ
methyl malonate under mild conditions and without partiꢀ
cipation of a C*ꢀstereocenter can be conveniently conꢀ
verted to the esters and amides of chiral unsaturated
carboxylic acids.39 Both enantiomers of the desymmetriꢀ
zation product of N,N´ꢀditosylꢀmesoꢀcyclopentꢀ4ꢀeneꢀ
1,3ꢀdiol biscarbamate are precursors of pharmacologiꢀ
cally active compounds Mannostatin A and (+)ꢀSwainsoꢀ
nine.40,41
Scheme 1
DCC stands for N,N´ꢀdicyclohexylcarbodiimide.

PdꢀCatalyzed asymmetric transformations
Russ.Chem.Bull., Int.Ed., Vol. 61, No. 10, October, 2012
1927
Scheme 2
Scheme 3
conversion of exoꢀ and endoꢀisomers of the second epimer
of complex 9 or the absence of one of them (see Ref. 46
and references cited therein).
To evaluate the stereodifferentiating ability of diamidoꢀ
phosphites 1 and 2, three model Pdꢀcatalyzed enantioꢀ
selective allylation reactions with (E)ꢀ1,3ꢀdiphenylallyl acꢀ
etate (10) were used, [Pd(allyl)Cl]2 served as a preꢀcatalꢀ
yst (Scheme 4, Tables 2—4). The allylation of sodium
pꢀtoluenesulfinate (Sꢀnucleophile) upon the action of 10
involving P*ꢀmonodentate ligand 1 resulted in sulfone
(R)ꢀ11 with moderate enantiomeric purity (ee 48%); the
optimal molar ratio L/Pd was equal to 2 (see Table 2,
entries 1 and 2). In the entries with the use of P*,Nꢀbidenꢀ
tate ligand 2, the product with the same absolute configuꢀ
ration and greater enantiomeric purity (ee to 68%) was
formed. In this case, the asymmetric induction virtually
did not depend on the molar ratio L/Pd, however, the
chemical yield was significantly higher when this ratio
increased to 2 (see Table 2, entries 3—5).
Scheme 4
The allylation of dimethyl malonate (Cꢀnucleophile)
upon the action of compound 10 using diamidophosphite 1
Table 1. The 31P NMR spectroscopic data (CDCl3)
for the ligands 1 and 2 and the values of their Tolꢀ
mann cone angles ()
BSA stands for bisꢀtrimethylsilylacetamide.
Comꢀ
pound

/deg
P
as the stereoselector proceeded with enantioselectivity up
to 40% (see Table 3, entries 1—4). the asymmetric inducꢀ
tion has proved slightly higher when the reaction was carꢀ
ried out in THF, while the highest conversion was obꢀ
1
2
120.3 (32%), 115.1 (68%)
129.8 (65%), 112.6 (35%)
151
146

1928
Russ.Chem.Bull., Int.Ed., Vol. 61, No. 10, October, 2012
Gavrilov et al.
Table 2. Data on the Pdꢀcatalyzed allylation of sodium pꢀtolueꢀ
nesulfinatea
Table 4. Data on the Pdꢀcatalyzed allylation of pyrrolidinea
Entry
Ligand L/Pd
Solvent
Conversion
(%)
ee (%)b
Entry
Ligand
L/Pd
Yield (%)
ee (%)b
1
2
3
4
5 c
1
1
2
2
2
1
2
1
2
1
25
40
50
90
27
14 (R)
48 (R)
67 (R)
68 (R)
60 (R)
1
2
3
4
5
6
7c
8
1
1
1
1
2
2
2
2
2
2
1
2
1
2
1
2
1
1
2
1
THF
THF
CH2Cl2
CH2Cl2
THF
THF
THF
CH2Cl2
CH2Cl2
CH2Cl2
32
61
100
100
90
95
43
100
100
100
13 (R)
31 (R)
2 (R)
3 (R)
67 (S)
71 (S)
43 (S)
65 (S)
55 (S)
50 (S)
a All the reactions were carried out at 20 C in THF, 48 h,
2 mol.% of [Pd(allyl)Cl]2.
b Enantiomeric excess of product 11 was determined by HPLC
9
10c
(Daicel Chiralcel OJ, C6H14—PriOH (4 : 1), 0.5 mL min–1
,
254 nm).
c Complex 9 was used.
a All the reactions were carried out at 20 C, 48 h, 2 mol.% of
[Pd(allyl)Cl]2.
b The conversion of substrate 10 and the enantiomeric excess of
product 13 were determined by HPLC (Daicel Chiralcel OD—H,
C6H14—PriOH—HNEt2 (200 : 1 : 0.1), 0.9 mL min–1, 254 nm).
c Complex 9 was used.
Table 3. Data on the Pdꢀcatalyzed allylation of dimethyl malꢀ
onatea
Entry Ligand L/Pd
Solvent
Conversion
(%)
ee (%)b
enantiomeric excess up to 71%, with the opposite (S)ꢀconꢀ
figuration and, as a rule, close to quantitative conversion
of the starting substrate 10 (see Table 4, entries 5—10).
Note that when the reaction was carried out in THF, an
increase in the molar ratio L/Pd to 2 led to a small inꢀ
crease in enantioselectivity, whereas in CH2Cl2, to its deꢀ
crease (see Table 4, entries 5, 6 and 8, 9).
The most efficient in allylation with (E)ꢀ1,3ꢀdiphenylꢀ
allyl acetate (10) P*,Nꢀbidentate ligand 2 was used in the
Pdꢀcatalyzed desymmetrization of N,N´ꢀditosylꢀmesoꢀ
cyclopentꢀ4ꢀeneꢀ1,3ꢀdiol biscarbamate (14) (Scheme 5,
Table 5).
1
2
3
4
5
6
7c
8
1
1
1
1
2
2
2
2
2
2
1
2
1
2
1
2
1
1
2
1
THF
THF
CH2Cl2
CH2Cl2
THF
THF
THF
CH2Cl2
CH2Cl2
CH2Cl2
20
47
52
100
85
98
11 (R)
40 (R)
9 (R)
30 (R)
81 (R)
83 (R)
97 (R)
79 (R)
76 (R)
40 (R)
67
98
99
55
9
10c
a All the reactions were carried out at 20 C, 48 h, 2 mol.% of
[Pd(allyl)Cl]2.
b The conversion of substrate 10 and the enantiomeric excess of
product 12 were determined by HPLC (Daicel Chiralcel ODꢀH,
C6H14—PriOH (99 : 1), 0.6 mL min–1, 254 nm).
c Complex 9 was used.
Scheme 5
served in CH2Cl2. Like in the asymmetric allylation of
sodium pꢀtoluenesulfinate, the greater enantioselectivity
was achieved at the molar ratio L/Pd equal to 2. Ligand 2
turned out to be an excellent stereoinductor: its participaꢀ
tion provided up to 97% ee (see Table 3, entries 5—10).
Tetrahydrofuran was the optimal solvent (see, for examꢀ
ple, entries 7 and 10). The molar ratio L/Pd virtually
did not influence enantioselectivity. The use of both
ligands 1 and 2 resulted in the formation of (R)ꢀenantioꢀ
mer of product 12.
When pyrrolidine was used as an Nꢀnucleophile, diaꢀ
midophosphite 1 provided not very high enantioselectivity
(31% ee), with the formed amine 13 having (R)ꢀconfiguꢀ
ration (see Scheme 4, Table 4, entries 1—4).
The highest asymmetric induction was observed in
THF and at the molar ratio L/Pd equal to 2. At the same
time, when ligand 2 was used, amine 13 was formed with
On the base of the literature data,47—49 [Pd2(dba)3]•
•CHCl3 and THF have been chosen as the optimal preꢀ
catalyst and solvent, respectively. At the molar ratio L/Pd

PdꢀCatalyzed asymmetric transformations
Russ.Chem.Bull., Int.Ed., Vol. 61, No. 10, October, 2012
1929
Table 5. Data on the Pdꢀcatalyzed desymmetrization of
compound 14a
chromatographs. Elemental analysis was performed in the
Laboratory of Organic Microanalysis of the A. N. Nesmeyanov
Institute of Organoelement Compounds, Russian Academy
of Sciences.
Entry
Ligand
L/Pd
Yield (%)
ee (%)b,c
All the reactions were performed under dry argon in anꢀ
hydrous solvents. The starting imino alcohol, (2S,3S)ꢀ2ꢀ(ferroꢀ
cenylideneamino)ꢀ3ꢀmethylpentanꢀ1ꢀol (7), was synthesized acꢀ
cording to the procedure described earlier.51 The starting subꢀ
strate, (E)ꢀ1,3ꢀdiphenylallyl acetate (10), as well as complexes
[Pd(allyl)Cl]2 and [Pd2(dba)3]•CHCl3, were obtained by the
known methods.52,53 Catalytic experiments of asymmetric allylꢀ
ation of sodium pꢀtoluenesulfinate, dimethyl malonate, and pyrꢀ
rolidine with the agent 10, as well as desymmetrization of subꢀ
strate 14, determination of conversion of 10 and enantiomeric
excess of products 11, 12, 13, and 16 were performed according
to the published procedures.25,27,54
1
2
2
2
1
2
83
68
61 (I)
44 (I)
a All the reactions were carried out at 35 C in THF, 24 h,
5 mol.% of [Pd2(dba)3]•CHCl3.
b Enantiomeric excess of product 16 was determined by
HPLC (Kromasil 5ꢀCelluCoat, C6H14—PriOH (9 : 1),
2 mL min–1, 219 nm, t(I) = 15 min, t(II) = 18 min).
c The absolute configuration of product 16 was not deꢀ
termined.
NꢀBocꢀLꢀisoleucine, N,N´ꢀdicyclohexylcarbodiimide (DCC),
adamantanꢀ1ꢀol, sodium pꢀtoluenesulfinate, dimethyl malonate,
bisꢀtrimethylsilylacetamide (BSA), pyrrolidine, mesoꢀcyclopentꢀ
4ꢀeneꢀ1,3ꢀdiol and tosyl isocyanate were commercial reactants
(Fluka and Aldrich).
equal to 1, product 16 was formed in good yield (83%) and
with enantioselectivity of 61% ee (see Table 5, entry 1).
To sum up the above data, the following conclusions
can be drawn. In general, P*ꢀmonodentate ligand 1 proꢀ
vided low or moderate asymmetric induction, up to
31—48% ee in the Pdꢀcatalyzed allylation of different
nucleophiles with (E)ꢀ1,3ꢀdiphenylallyl acetate. Howevꢀ
er, it is significantly more efficient than the known monoꢀ
cyclic diamidophosphites LE and LF, whose involvement,
as it has been already noted, in the Pdꢀ and Irꢀcatalyzed
allylation of dimethyl malonate resulted in virtually raꢀ
cemic products. It is necessary to note that these phosphaꢀ
cyclanes were more diastereomerically pure than 1: LE
was individual stereo isomer, whereas LF was a mixture of
epimers at the P*ꢀstereocenter in the ratio 1 : 2.5.33,50 This
indicated substantial asymmetrization potential of diamidoꢀ
phosphites with 1,3,2ꢀdiazaphospholidine ring derived
from (2S,3S)ꢀN2,3ꢀdimethylꢀN1ꢀphenylpentaneꢀ1,2ꢀdiꢀ
amine. Thus, diamidophosphite 2 is efficient enough
stereoselector. Taking into account virtually identical steric
requirements and diastereomeric composition of 1 and 2,
it can be suggested that this is due to the bidentate nature
of ligand 2. The presence of additional C*ꢀstereocenters in
the composition of the exocyclic substituent in compound 2
should also be taken into account.
tertꢀButyl (2S,3S)ꢀ3ꢀmethylꢀ1ꢀoxoꢀ1ꢀ(phenylamino)pentylꢀ
2ꢀcarbamate (5). N,N´ꢀDicyclohexylcarbodiimide (3.43 g,
16.6 mmol) was added in small portions to a vigorously stirred
solution of NꢀBocꢀLꢀisoleucine (3.49 g, 15.1 mmol) and aniline
(1.93 mL, 21.1 mmol) in CH2Cl2 (25 mL) at 20 C. The mixture
obtained was stirred for 16 h at 20 C and filtered through Celite,
the solvent was evaporated at reduced pressure (40 Torr). The
product was purified by flashꢀchromatography on silica gel (eluꢀ
ent hexane—ethyl acetate (1 : 4)) with subsequent crystallization
from heptane. The yield was 3.52 g (76%), white powder, m.p.
139—140 C, []25D –33.4 (c 1.0, CHCl3). Found (%): C, 66.78;
H, 8.61; N, 9.07. C17H26N2O3. Calculated (%): C, 66.64;
H, 8.55; N, 9.14. 1H NMR (CDCl3), : 0.91 (t, 3 H, 3J = 7.4 Hz);
0.99 (d, 3 H, 3J = 6.8 Hz); 1.18 (m, 2 H); 1.43 (s, 9 H); 1.96
(br.m, 1 H); 4.09 (br.m, 1 H); 5.24 (br.d, 1 H, 3J = 8.8 Hz); 7.06
3
(t, 1 H, 3J = 7.4 Hz); 7.24 (t, 2 H, J = 7.5 Hz); 7.48 (d, 2 H,
3J = 7.8 Hz); 8.28 (br.s, 1 H). MS (EI), m/z (Irel (%)): 306 [M]+
(8), 130 [M – Boc – Ph + 2 H]+ (87), 93 [PhNH2]+ (100).
(2S,3S)ꢀN2,3ꢀDimethylꢀN1ꢀphenylpentaneꢀ1,2ꢀdiamine (3).
Amide 5 (3.31 g, 10.8 mmol) was added in small portions to
a vigorously stirred suspension of LiAlH4 (1.02 g, 27 mmol) in
THF (50 mL) at 0 C. The mixture obtained was heated to the
boiling point and refluxed for 8 h, cooled to 0 C, followed by
a slow dropwise addition of 15% aqueous KOH (2 mL). The
resulted suspension was heated to the boiling point and refluxed
for 30 min, cooled to 20 C and filtered. A precipitate formed
was washed on the filter with THF (2×20 mL) and CH2Cl2
(2×20 mL). The solvents were evaporated from the combined
filtrates at reduced pressure (40 Torr), the residue was distilled
in vacuo (1 Torr). The yield was 1.58 g (71%), slightly yellow
light oil, b.p. 110—111 C, []25D +9.2 (c 1.0, CHCl3). Found (%):
C, 75.93; H, 10.89; N, 13.67. C13H22N2. Calculated (%):
C, 75.68; H, 10.75; N, 13.58. 13C NMR (CDCl3), : 11.8 (s, Me);
13.9 (s, Me); 26.2 (s, CH2); 33.6 (s, MeN); 34.7 (s, CH); 42.9
(s, CH2N); 62.2 (s, CHN); 112.7 (s, CHPh); 116.9 (s, CHPh); 128.9
Experimental
31
1
P, H, and 13C NMR spectra were recorded on a Bruker
Avance 400 (161.98, 400.13 and 100.61 MHz) spectrometer relꢀ
ative to 85% H3PO4 in D2O or Me4Si. Signals in the 13C NMR
spectra were assigned using the DEPT procedure. Mass spectra
with electron impact ionization (EI, 70 eV) were obtained on
a Varian MATꢀ311 instrument, with laser desorption ionization
(MALDI TOF/TOF), on a Bruker Daltonics Ultraflex inꢀ
strument, with electrospray ionization (ESI), on a Finnigan
LCQ Advantage instrument. Optical rotation was measured on
a Perkin—Elmer 341 polarimeter. Specific rotation is given in
1
(s, CHPh); 148.7 (s, CPh). H NMR (CDCl3), : 0.88 (d, 3 H,
3J = 6.8 Hz); 0.94 (t, 3 H, 3J = 7.4 Hz); 1.27 (m, 1 H); 1.47
(m, 1 H); 1.71 (m, 1 H); 1.75 (br.s, 1 H); 2.39 (s, 3 H); 2.55
(m, 1 H); 2.86 (m, 1 H); 3.16 (m, 1 H); 4.20 (br.s, 1 H); 6.63
deg mL g–1 dm–1 and concentration of solutions in g (100 mL)–1
.
Analysis of enantiomeric purity of products of the catalytic reacꢀ
tions was performed on HP Agilent 1100 and Stayer HPLCꢀ
3
(d, 2 H, J = 7.6 Hz); 6.68 (t, 1 H, 3J = 7.5 Hz); 7.17 (t, 2 H,

1930
Russ.Chem.Bull., Int.Ed., Vol. 61, No. 10, October, 2012
Gavrilov et al.
3J = 7.6 Hz). MS (EI), m/z (Irel (%)): 207 [M + H]+ (15), 107
[PhNHMe]+ (100).
(br.s, 6 H); 1.79 (m, 2 H); 1.92 (br.s, 4 H); 2.09 (m, 1 H); 2.13
(br.s, 3 H); 2.77 (d, 3 H, 3J = 13.2 Hz); 3.21 (m, 1 H); 3.39
(m, 1 H); 3.57 (m, 1 H); 6.66 (t, 1 H, 3J = 7.8 Hz); 7.0 (br.d, 2 H,
3J = 8.0 Hz); 7.23 (m, 2 H) (minor epimer). MS (MALDI
TOF/TOF), m/z (Irel (%)): 387 [M + H]+ (100), 207
[PhNHCH2CH(Busec)NHMe + H]+ (42), 136 [C10H16]+ (11).
(2´S,3´S,4S)ꢀ4ꢀsecꢀButylꢀ2ꢀ[3´ꢀmethylꢀ2´ꢀ(ferrocenylideneꢀ
amino)pentyloxy]ꢀ3ꢀmethylꢀ1ꢀphenylꢀ1,3,2ꢀdiazaphospholidine
(2). The yield was 1.77 g (81%), viscous red oil. Found (%):
C, 66.02; H, 7.69; N, 7.82. C30H42FeN3OP. Calculated (%):
C, 65.81; H, 7.73; N, 7.68. 13C NMR (CDCl3)), : 11.1 (s, Me);
12.3 (s, Me); 12.5 (s, Me); 16.0 (s, Me); 25.4 (s, CH2); 27.3
(4S)ꢀ4ꢀsecꢀButylꢀ2ꢀchloroꢀ3ꢀmethylꢀ1ꢀphenylꢀ1,3,2ꢀdiazaꢀ
phospholidine (8). A solution of diamine 3 (2.06 g, 10 mmol) in
benzene (50 mL) was added slowly dropwise to a vigorously
stirred solution of PCl3 (0.88 mL, 10 mmol) and Et3N (3.06 mL,
22 mmol) in benzene (100 mL) at 0 C. A formation of rich clayꢀ
colored precipitate was observed. The suspension obtained was
heated to the boiling point and refluxed for 5 min, cooled to
20 C, a precipitate of Et3N•HCl was filtered off. The filtrate
was concentrated in vacuo (40 Torr) and the residue was distilled
in vacuo (1 Torr). The yield was 1.87 g (69%), slightly yellow
paraffinꢀlike oil, b.p. 204—207 C (bath). Found (%): C, 58.02;
H, 7.25; N, 10.58. C13H20ClN2P. Calculated (%): C, 57.67;
H, 7.45; N, 10.35. 13C NMR (CDCl3), : 11.5 (s, Me); 12.2 (s, Me);
2
(s, CH2); 33.7 (d, MeN, JC,P = 40.8 Hz); 35.3 (s, CH); 36.3
3
2
(d, CH, JC,P = 6.0 Hz); 48.1 (d, CH2N, JC,P = 7.5 Hz); 64.4
(d, CH2O, 2JC,P = 8.3 Hz); 65.5 (d, CHN, 2JC,P = 12.1 Hz); 68.1
(s, CHFc); 68.9 (s, CHFc); 69.0 (s, CCp); 69.9 (s, CHFc); 70.0
2
27.2 (s, CH2); 30.8 (d, MeN, JC,P = 19.6 Hz); 33.5 (d, CH,
3JC,P = 3.8 Hz); 48.2 (d, CH2N, 2JC,P = 9.1 Hz); 65.8 (d, CHN,
(s, CHFc); 77.1 (s, CHN); 80.6 (s, CFc); 115.5 (d, CHPh
3JC,P = 13.6 Hz); 119.0 (d, CHPh 4JC,P = 2.3 Hz); 129.1
(s, CHPh); 146.1 (d, CPh
2JC,P = 13.8 Hz); 160.6 (s, CH=N)
,
2JC,P = 10.6 Hz); 116.3 (d, CHPh
,
3JC,P = 15.9 Hz); 121.3
,
(d, CHPh
,
4JC,P = 2.3 Hz); 129.2 (s, CHPh); 142.8 (d, CPh
,
,
2JC,P = 15.0 Hz). 1H NMR (CDCl3), : 0.87 (d, 3 H, 3J = 6.8 Hz);
1.0 (t, 3 H, 3J = 7.8 Hz); 1.25 (m, 1 H); 1.38 (m, 1 H); 1.88 (m, 1 H);
(predominant epimer) and 11.0 (s, Me); 12.1 (s, Me); 12.6
(s, Me); 16.1 (s, Me); 25.2 (s, CH2); 26.9 (s, CH2); 30.2 (d, MeN,
3
3
2.72 (d, 3 H, J = 16.1 Hz); 3.46 (m, 1 H); 3.61 (m, 1 H); 3.68
2JC,P = 20.4 Hz); 34.3 (d, CH, JC,P = 3.0 Hz); 36.4 (s, CH);
(m, 1 H); 6.97 (t, 1 H, 3J = 7.2 Hz); 7.07 (m, 2 H); 7.30 (t, 2 H,
3J = 7.8 Hz). MS (EI), m/z (Irel (%)): 270 [M]+ (57), 235 [M – Cl]+
(100).
48.1 (d, CH2N, 2JC,P = 7.5 Hz); 65.6 (s, CH2O); 66.6 (d, CHN,
2JC,P = 9.8 Hz); 68.2 (s, CHFc); 68.8 (s, CHFc); 69.1 (s, CCp);
70.1 (s, CHFc); 70.2 (s, CHFc); 77.0 (s, CHN); 80.5 (s, CFc);
114.7 (d, CHPh, 3JC,P = 14.3 Hz); 118.9 (d, CHPh, 4JC,P = 1.5 Hz);
Preparation of diamidophosphite ligands 1 and 2 (general proꢀ
cedure). A solution of adamantanol 6 or iminoalcohol 7 (4 mmol)
in toluene (10 mL) was added slowly dropwise to a vigorously
stirred solution of phosphorylating agent 8 (1.08 g, 4 mmol) and
Et3N (0.61 mL, 4.4 mmol) in toluene (10 mL) at 0 C. The
mixture obtained was heated to the boiling point and refluxed for
10 min, cooled to 20 C, a precipitate of Et3N•HCl was filtered
off. The filtrate was concentrated in vacuo (40 Torr). The prodꢀ
ucts 1 and 2 were purified by flashꢀchromatography on alumina
and silica gel, respectively, eluent toluene.
2
129.0 (s, CHPh); 145.2 (d, CPh, JC,P = 14.5 Hz); 160.8
(s, CH=N) (minor epimer). 1H NMR (CDCl3), : 0.75 (d, 3 H,
3J = 6.6 Hz); 0.88 (t, 3 H, 3J = 7.2 Hz); 0.94 (d, 3 H, 3J = 6.8 Hz);
0.98 (t, 3 H, 3J = 7.7 Hz); 1.21 (m, 2 H); 1.41 (m, 2 H); 1.62
(m, 1 H); 1.78 (m, 1 H); 2.67 (d, 3 H, 3J = 13.2 Hz); 2.80 (m, 1 H);
3.27 (m, 1 H); 3.51 (m, 2 H); 3.76 (m, 1 H); 4.0 (m, 1 H); 4.16
(s, 5 H); 4.31 (m, 2 H); 4.59 (m, 2 H); 6.83 (t, 1 H, 3J = 7.6 Hz);
7.05 (br.m, 2 H); 7.20 (m, 2 H); 7.84 (s, 1 H) (predominant
epimer) and 0.80 (d, 3 H, 3J = 6.7 Hz); 0.89 (t, 3 H, 3J = 7.3 Hz);
0.96 (d, 3 H, 3J = 6.8 Hz); 1.01 (t, 3 H, 3J = 7.6 Hz); 1.21 (m, 2 H);
1.43 (m, 2 H); 1.63 (m, 1 H); 1.80 (m, 1 H); 2.62 (d, 3 H,
3J = 13.2 Hz); 2.82 (m, 1 H); 3.29 (m, 1 H); 3.51 (m, 2 H); 3.78
(m, 1 H); 4.02 (m, 1 H); 4.20 (s, 5 H); 4.32 (m, 2 H); 4.61
(m, 2 H); 6.83 (t, 1 H, 3J = 7.6 Hz); 7.05 (br.m, 2 H); 7.21
(m, 2 H); 7.95 (s, 1 H) (minor epimer). MS (MALDI
TOF/TOF), m/z (Irel (%)): 566 [M + H + H2O]+ (28), 402
[M – CpFe(C5H4) + H + K]+ (100), 363 [M – CpFe(C5H4) + H]+
(11). MS (ESI), m/z (Irel (%)): 548 [M + H]+ (27), 235 [M –
– C17H22FeNO]+ (100).
(4S)ꢀ4ꢀsecꢀButylꢀ3ꢀmethylꢀ1ꢀphenylꢀ2ꢀ(tricyclo[3.3.1.13´,7´]ꢀ
decyloxyꢀ1´)ꢀ1,3,2ꢀdiazaphospholidine (1). The yield was 1.31 g
(85%), colorless oil. Found (%): C, 71.62; H, 9.23; N, 7.19.
C23H35N2OP. Calculated (%): C, 71.47; H, 9.13; N, 7.25.
13C NMR (CDCl3), : 11.4 (s, Me); 12.6 (s, Me); 27.5 (s, CH2);
2
31.0 (s, C(3´), C(5´), C(7´)); 31.1 (d, MeN, JC,P = 13.6 Hz);
34.1 (d, CH, 3JC,P = 3.8 Hz); 36.2 (s, C(4´), C(6´), C(10´)); 45.3
3
(d, C(2´), C(8´), C(9´), JC,P = 7.5 Hz),; 47.3 (d, CH2N,
2JC,P = 8.3 Hz); 63.5 (d, CHN, 2JC,P = 9.8 Hz); 73.5 (d, C(1´),
2JC,P = 6.8 Hz); 114.8 (d, CHPh 3JC,P = 15.8 Hz); 118.2
,
(d, CHPh
,
4JC,P = 2.3 Hz); 128.9 (s, CHPh); 145.6 (d, CPh
,
{(2´S,3´S,4S)ꢀ4ꢀsecꢀButylꢀ2ꢀ[3´ꢀmethylꢀ2´ꢀ(ferrocenylꢀ
ideneamino)pentyloxy]ꢀ3ꢀmethylꢀ1ꢀphenylꢀ1,3,2ꢀdiazaphosphoꢀ
lidineꢀP,N}(ꢀallyl)palladium(2+) tetrafluoroborate (9). A soluꢀ
tion of P*,Nꢀbidentate ligand 2 (0.110 g, 0.2 mmol) in CH2Cl2
(2 mL) was added dropwise to a stirred solution of [Pd(All)Cl]2
(0.037 g, 0.1 mmol) in CH2Cl2 (1 mL) at 20 C over 30 min. The
reaction mixture was stirred for another 1 h at 20 C. A solution
of AgBF4 (0.039 g, 0.2 mmol) in THF (2 mL) was added dropꢀ
wise to the solution obtained over 30 min and the reaction mixꢀ
ture was stirred for 1.5 h at 20 C. A precipitate of AgCl was
filtered off. Excess of solvents was evaporated at reduced presꢀ
sure (40 Torr) to ~0.5 mL, followed by the addition of diethyl
ether (7 mL). A precipitate formed was separated by centrifugaꢀ
tion, washed with diethyl ether (2×5 mL), dried in air and in vacuo
(1 Torr). The yield was 0.145 g (93%), red powder, m.p.
114—117 C (with decomp.). Found (%): C, 51.01; H, 5.92;
2JC,P = 17.1 Hz) (predominant epimer) and 12.5 (s, Me); 13.2
(s, Me); 27.1 (s, CH2); 30.8 (s, C(3´), C(5´), C(7´)); 31.3
2
3
(d, MeN, JC,P = 29.5 Hz); 33.5 (d, CH, JC,P = 6.0 Hz); 36.3
(s, C(4´), C(6´), C(10´)); 45.2 (d, C(2´), C(8´), C(9´), JC,P
3
=
2
= 7.5 Hz); 47.7 (d, CH2N, JC,P = 8.3 Hz); 67.9 (d, CHN,
2JC,P = 10.6 Hz); 73.7 (d, C(1´), JC,P = 5.3 Hz); 116.0 (d,
2
CHPh, 3JC,P = 13.6 Hz); 118.4 (d, CHPh, 4JC,P = 2.3 Hz); 129.3
(s, CHPh); 144.9 (d, CPh
,
2JC,P = 15.5 Hz) (minor epimer).
1H NMR (CDCl3), : 0.81 (d, 3 H, J = 6.9 Hz); 0.97 (t, 3 H,
3J = 7.8 Hz); 1.22 (m, 1 H); 1.42 (m, 1 H); 1.63 (br.s, 6 H); 1.79
(m, 2 H); 1.92 (br.s, 4 H); 2.09 (m, 1 H); 2.13 (br.s, 3 H); 2.55
(d, 3 H, 3J = 16.2 Hz); 3.11 (m, 1 H); 3.51 (m, 1 H); 3.59 (m, 1 H);
6.81 (t, 1 H, 3J = 7.5 Hz); 7.02 (br.d, 2 H, 3J = 8.1 Hz); 7.23
(m, 2 H) (predominant epimer) and 0.94 (d, 3 H, 3J = 7.0 Hz);
1.01 (t, 3 H, 3J = 7.7 Hz); 1.24 (m, 1 H); 1.45 (m, 1 H); 1.63
3

PdꢀCatalyzed asymmetric transformations
Russ.Chem.Bull., Int.Ed., Vol. 61, No. 10, October, 2012
1931
N, 5.20. C33H47BF4FeN3OPPd. Calculated (%): C, 50.70;
H, 6.06; N, 5.37. MS (MALDI TOF/TOF), m/z (Irel (%)): 694
[M – BF4]+ (17), 653 [M – All – BF4]+ (100).
mixture obtained was stirred for 15 min at 20 C, then heated to
55 C and stirred for at this temperature for 1 h and cooled to
20 C). The reaction mixture was stirred for 24 h. The solvent
was evaporated at reduced pressure (40 Torr), the residue was
purified by flashꢀchromatography on silica gel (eluent hexꢀ
ane—ethyl acetate (4 : 1)). The product 16 was obtained as slightꢀ
Asymmetric allylation of sodium pꢀtoluenesulfinate with
(E)ꢀ1,3ꢀdiphenylallyl acetate (10). A solution of [Pd(allyl)Cl]2
(0.0037 g, 0.01 mmol) and the corresponding ligand (0.02 mmol
or 0.04 mmol) in THF (5 mL) was stirred for 40 min or a preꢀ
prepared complex 9 (0.0156 g, 0.02 mmol) was dissolved in THF
(5 mL). Then, (E)ꢀ1,3ꢀdiphenylallyl acetate (0.1 mL, 0.5 mmol)
was added and the solution was stirred for another 15 min, folꢀ
lowed by the addition of sodium pꢀtoluenesulfinate (0.178 g,
1 mmol). The reaction mixture was stirred for 48 h, quenched
with saturated aq. NaCl (5 mL), stirred for 1 h, and extracted
with THF (3×2 mL). The organic phase was washed with satuꢀ
rated aq. NaCl (2×2 mL), dried with MgSO4, and filtered through
Celite. The solvent was evaporated at reduced pressure (40 Torr)
and the residue obtained was recrystallized from 95% ethanol.
The milkꢀwhite crystals of product 11 were dried in vacuo
(10 Torr). The IR spectrum and the 1H NMR spectrum were in
complete correspondence with those published earlier.55 The
enantiomeric excess of product 11 was determined by HPLC on
a chiral stationary phase.
Asymmetric allylation of dimethyl malonate with (E)ꢀ1,3ꢀ
diphenylallyl acetate. A solution of [Pd(allyl)Cl]2 (0.0037 g,
0.01 mmol) and the corresponding ligand (0.02 mmol or
0.04 mmol) in the corresponding solvent (5 mL) was stirred for
40 min a preꢀprepared complex 9 (0.0156 g, 0.02 mmol) was
dissolved in the corresponding solvent (5 mL). After addition of
(E)ꢀ1,3ꢀdiphenylallyl acetate (0.1 mL, 0.5 mmol), the solution
was stirred for another 15 min, then dimethyl malonate (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 evaporated at reduced pressure (40 Torr), the resiꢀ
due was dried in vacuo (10 Torr). The conversion of substrate 10
and the enantiomeric excess of product 12 were determined by
HPLC on a chiral stationary phase.
Asymmetric allylation of pyrrolidine with (E)ꢀ1,3ꢀdiphenylꢀ
allyl acetate. A solution of [Pd(allyl)Cl]2 (0.0037 g, 0.01 mmol)
and the corresponding ligand (0.02 mmol or 0.04 mmol) in the
corresponding solvent (5 mL) was stirred for 40 min or a preꢀ
prepared complex 9 (0.0156 g, 0.02 mmol) was dissolved in the
corresponding solvent (5 mL). After addition of (E)ꢀ1,3ꢀdipheꢀ
nylallyl acetate (0.1 mL, 0.5 mmol), the solution was stirred for
another 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 evaporated at reduced pressure (40 Torr), the resiꢀ
due was dried in vacuo (10 Torr). The conversion of substrate 10
and the enantiomeric excess of product 13 were determined by
HPLC on a chiral stationary phase.
Desymmetrization of N,N´ꢀditosylꢀmesoꢀcyclopentꢀ4ꢀeneꢀ
1,3ꢀdiol biscarbamate (14). A solution of [Pd2(dba)3]•CHCl3
(0.005 g, 0.005 mmol) and ligand 2 (0.0055 g, 0.01 mmol or
0.011 g, 0.02 mmol) in THF (1 mL) was stirred for 40 min. The
solution obtained was heated to 35 C, followed by the addition
of a solution of N,N´ꢀditosylꢀmesoꢀcyclopentꢀ4ꢀeneꢀ1,3ꢀdiol bisꢀ
carbamate (14) and Et3N (14 L, 0.099 mmol) in THF (0.5 mL)
(the substrate 14 was prepared in situ as follows: tosyl isocyanate
(35 L, 0.232 mmol) was added to a solution of mesoꢀcyclopentꢀ
4ꢀeneꢀ1,3ꢀdiol (0.01 g, 0.099 mmol) (15) in THF (0.5 mL), the
1
ly brown solid substance. The IR spectrum and the H and 13C
NMR spectra of compound 16 were in complete corresponꢀ
dence with those published earlier.47 The enantiomeric excess of
product 16 was determined by HPLC on a chiral stationary phase.
This work was financially supported by the Russian
Foundation for Basic Research (Project Nos 11ꢀ03ꢀ00347ꢀa
and 12ꢀ03ꢀ31205ꢀmolꢀa).
References
1. J. M. Brown, in Comprehensive Asymmetric Catalysis, Eds
E. N. Jacobsen, A. Pfaltz, Y. Yamamoto, Springer, Berlin,
1999, Vol. 1, p. 121.
2. T. Ohkuma, M. Kitamura, R. Noyori, in Catalytic Asymmetꢀ
ric Synthesis, Ed. I. Ojima, WileyꢀVCH, New York, 2000, p. 1.
3. M. J. Burk, Acc. Chem. Res., 2000, 33, 363.
4. H.ꢀU. Blaser, E. Schmidt, in Asymmetric Catalysis on Indusꢀ
trial Scale, WileyꢀVCH, Weinheim, 2004.
5. I. P. Beletskaya, M. M. Kabachnik, Mendeleev Commun.,
2008, 18, 113.
6. K. Yu. Koltunov, Enantioselektivnyi sintez organicheskikh
soedinenii [Enantioselective Synthesis of Organic Comꢀ
pounds], Novosibirsk State Univ., Novosibirsk, 2010, 41 pp.
(in Russian).
7. C. A. Falciola, A. Alexakis, Eur. J. Org. Chem., 2008, 3765.
8. G. C. Hargaden, P. J. Guiry, Chem. Rev., 2009, 109, 2505.
9. A. Börner, in Phosphorus Ligands in Asymmetric Catalysis,
Ed. A. Börner, WileyꢀVCH, Weinheim, 2008, Vol. 1, p. 28.
10. M. Diéguez, A. Ruiz, C. Claver, Dalton Trans., 2003, 2957.
11. A. G. Tolstikov, T. B. Khlebnikova, G. A. Tolstikov, Khimiya
i komp´yuternoe modelirovanie. Butlerovskie soobshcheniya
[Chemistry and Computor Simulation. Butlerov Communicaꢀ
tion], 2002, 27 (in Russian).
12. A. G. Tolstikov, T. B. Khlebnikova, O. V. Tolstikova, G. A.
Tolstikova, Russ. Chem. Rev., 2003, 72, 803.
13. J. F. Teichert, B. L. Feringa, Angew. Chem., Int. Ed., 2010,
49, 2486.
14. Q.ꢀL. Zhou, in Privileged Chiral Ligands and Catalysts,
Ed. Q.ꢀL. Zhou, WileyꢀVCH, Weinheim, 2011.
15. J. Ansel, M. Wills, Chem. Soc. Rev., 2002, 31, 259.
16. A. Alexakis, C. Benhaim, Eur. J. Org. Chem., 2002, 19, 3221.
17. O. Molt, T. Shrader, Synthesis, 2002, 2633.
18. K. N. Gavrilov, O. G. Bondarev, A. I. Polosukhin, Russ.
Chem. Rev., 2004, 73, 671.
19. M. T. Reetz, G. Mehler, A. Meiswinkel, T. Sell, Tetrahedron
Lett., 2002, 43, 7941.
20. B. H. G. Swennenhuis, R. Chen, P. W. N. M. van Leeuwen,
J. G. de Vries, P. C. J. Kamer, Eur. J. Org. Chem., 2009,
5796.
21. G. Buono, N. Toselli, D. Martin, in Phosphorus Ligands in
Asymmetric Catalysis, Ed. A. Börner, WileyꢀVCH, Weinheim,
2008, Vol. 2, p. 529.
22. M. T. Reetz, H. Oka, R. Goddard, Synthesis, 2003, 1809.

1932
Russ.Chem.Bull., Int.Ed., Vol. 61, No. 10, October, 2012
Gavrilov et al.
23. J. M. Brunel, T. Constantieux, G. Buono, J. Org. Chem.,
1999, 64, 8940.
24. G. Delapierre, J. M. Brunel, T. Constantieux, G. Buono,
Tetrahedron: Asymmetry, 2001, 12, 1345.
25. 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.
26. 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.
42. P. Pelagatti, M. Carcelli, F. Calbiani, C. Cassi, L. Elviri,
C. Pelizzi, U. Rizzotti, D. Rogolino, Organometallics, 2005,
24, 5836.
43. K. Barta, M. Hölscher, G. Franciò, W. Leitner, Eur. J. Org.
Chem., 2009, 4102.
44. C. A. Tolman, Chem. Rev., 1977, 77, 313.
45. A. I. Polosukhin, A. Yu. Kovalevskii, K. N. Gavrilov, Koorꢀ
dinats. Khim., 1999, 25, 812 [Russ. J. Coord. Chem.
(Engl. Transl.), 1999, 25, 758].
46. K. N. Gavrilov, V. N. Tsarev, S. I. Konkin, S. E. Lyubimov,
A. A. Korlyukov, M. Yu. Antipin, V. A. Davankov, Eur. J.
Inorg. Chem., 2005, 3311.
27. K. N. Gavrilov, S. V. Zheglov, M. N. Gavrilova, I. M. Noviꢀ
kov, M. G. Maksimova, N. N. Groshkin, E. A. Rastorguev,
V. A. Davankov, Tetrahedron, 2012, 68, 1581.
28. M. Kimura, Y. Uozumi, J. Org. Chem., 2007, 72, 707.
29. E. B. Benetskiy, C. Bolm, Tetrahedron: Asymmetry, 2011,
22, 373.
47. B. M. Trost, D. L. Van Vranken, C. Bingel, J. Am. Chem.
Soc., 1992, 114, 9327.
48. S. Carboni, L. Pignataro, C. Gennari, U. Piarulli, Tetraꢀ
hedron: Asymmetry, 2009, 20, 1185.
49. V. Benessere, A. De Roma, R. D. Litto, M. Lega, F. Ruffo,
Eur. J. Org. Chem., 2011, 5779.
30. O. G. Bondarev, R. Goddard, Tetrahedron Lett., 2006,
47, 9013.
50. A. Alexakis, S. Mutti, J. F. Normant, J. Am. Chem. Soc.,
1991, 113, 6332.
31. R. Mariz, A. Briceno, R. Dorta, Organometallics, 2008,
27, 6605.
32. I. S. Mikhel, G. Bernardinelli, A. Alexakis, Inorg. Chim.
Acta, 2006, 359, 1826.
33. B. Bartets, C. GarciaꢀYebra, G. Helmchen, Eur. J. Org.
Chem., 2003, 1097.
34. K. V. L. Crepy, T. Imamoto, Adv. Synth. Catal., 2003,
345, 79.aaa
35. Z. Lu, S. Ma, Angew. Chem., Int. Ed., 2008, 47, 258.
36. M. Dieguez, O. Pamies, Acc. Chem. Res., 2010, 43, 312.
37. H. FernandezꢀPerez, P. Etayo, A. Panossian, A. VidalꢀFerꢀ
ran, Chem. Rev., 2011, 111, 2119.
38. J. Magano, Tetrahedron, 2011, 67, 7875.
39. D. Lafrance, P. Bowles, K. Leeman, R. Rafka, Org. Lett.,
2011, 13, 2322.
51. K. N. Gavrilov, O. G. Bondarev, R. V. Lebedev, A. A.
Shiryaev, S. E. Lyubimov, A. I. Polosukhin, G. V. Grintꢀ
selevꢀKnyazev, K. A. Lyssenko, S. K. Moiseev, N. S. Ikonꢀ
nikov, V. N. Kalinin, V. A. Davankov, A. V. Korostylev,
H.ꢀJ. Gais, Eur. J. Inorg. Chem., 2002, 1367.
52. P. R. Auburn, P. B. McKenzie, B. Bosnich, J. Am. Chem.
Soc., 1985, 107, 2033.
53. T. Ukai, H. Kawazura, Y. Ishii, J. Organomet. Chem., 1974,
65, 253.
54. K. N. Gavrilov, S. E. Lyubimov, S. V. Zheglov, E. B.
Benetsky, V. A. Davankov, J. Mol. Catal. A, 2005, 231, 255.
55. D. Seebach, E. Devaquet, A. Emst, M. Hayakawa, F. N. M.
Kiihnle, W. B. Schweizer, B. Weher, Helv. Chim. Acta, 1995,
78, 1636.
40. B. M. Trost, M. L. Crawley, Chem. Rev., 2003, 103, 2921.
41. T. Graening, H.ꢀG. Schmalz, Angew. Chem., Int. Ed., 2003,
42, 2580.
Received April 25, 2012;
in revised form September 4, 2012