Asymmetric catalytic reactions using P*-mono-, P*,N- and P*,P*-bidentate diamidophosphites with BINOL backbones and 1,3,2-diazaphospholidine moieties: Differences in the enantioselectivity

Article abstract of DOI:10.1002/adsc.201000325

A new series of P*-chiral diamidophosphites with 1,3,2- diazaphospholidine rings, based on (S_a)- or (R_a)-BINOL and their easily accessible derivatives, has been synthesized for the first time and tested in asymmetric transition metal catalysis. Up to 99% ee was achieved in the rhodium-catalyzed asymmetric hydrogenation of functionalized olefins and in the palladium-catalyzed allylic substitution. The influence of the nature of the donor atoms and denticity on the asymmetric induction is discussed. In addition, the first example of a successful platinum-catalyzed asymmetric allylic amination (up to 86% ee) with participation of organophosphorus ligands is considered.

Full text of DOI:10.1002/adsc.201000325

FULL PAPERS
DOI: 10.1002/adsc.201000325
Asymmetric Catalytic Reactions Using P*-Mono-, P*,N- and
P*,P*-Bidentate Diamidophosphites with BINOL Backbones
and 1,3,2-Diazaphospholidine Moieties: Differences in the
Enantioselectivity
Konstantin N. Gavrilov,a,* Sergey V. Zheglov,a Eugenie A. Rastorguev,b
Nikolay N. Groshkin,a Marina G. Maksimova,a Eduard B. Benetsky,b
Vadim A. Davankov,b and Manfred T. Reetzc,*
a
Department of Chemistry, Ryazan State University, Svoboda Str. 46, 390000 Ryazan, Russia
Fax : (+7)-495-135-6471; e-mail: k.gavrilov@rsu.edu.ru
Institute of Organoelement Compounds, Russian Academy of Sciences, Vavilov Str. 28, 119991 Moscow, Russia
Max-Planck-Institut fꢀr Kohlenforschung, Kaiser-Wilhelm-Platz 1, 45470 Mꢀlheim an der Ruhr, Germany
b
c
Fax : (+49)-208-306-2985; e-mail: reetz@mpi-muelheim.mpg.de
Received: April 27, 2010; Revised: July 28, 2010; Published online: September 15, 2010
Supporting information for this article is available on the WWW under
http://dx.doi.org/10.1002/adsc.201000325.
Abstract: A new series of P*-chiral diamidophos- ty on the asymmetric induction is discussed. In addi-
phites with 1,3,2-diazaphospholidine rings, based on tion, the first example of a successful platinum-cata-
(Sa)- or (Ra)-BINOL and their easily accessible de- lyzed asymmetric allylic amination (up to 86% ee)
rivatives, has been synthesized for the first time and with participation of organophosphorus ligands is
tested in asymmetric transition metal catalysis. Up to considered.
99% ee was achieved in the rhodium-catalyzed asym-
metric hydrogenation of functionalized olefins and in
the palladium-catalyzed allylic substitution. The in- Keywords: asymmetric catalysis; palladium; plati-
fluence of the nature of the donor atoms and dentici- num; P ligands; rhodium
Introduction
and/or electronic features (modules) that may be
varied readily in a systematic fashion, in order to opti-
Asymmetric catalysis is now regarded as one of the mize the design for a given purpose. A design is infor-
most cost-effective and environmentally viable meth- mative to the extent that variations in the ligand mod-
ods for the production of a truly vast array of struc- ules can be correlated to changes in the reactivity or
turally diverse, enantiomerically pure compounds. In selectivity of the catalyst.[1c,2] The set of such powerful
addition to the well-known applications in pharma- modules includes the nature of the donor atoms and
ceutical chemistry, this method is successfully used in denticity. The majority of very important and widely
the synthesis of fragrance compounds, plant protec- used chiral ligands bear phosphorus and/or nitrogen
tion chemicals, individual stereoisomeric polymers, donor atoms. The p-acceptor character of phosphorus
and liquid crystals.[1] One of the core research activi- can stabilize a metal centre in a low oxidation state,
ties in the field of asymmetric catalysis is the ongoing while the nitrogen s-donor ability makes the metal
development of new ligands to achieve higher levels more susceptible to oxidative addition reactions. This
of efficiency and selectivity to meet the increasing de- can help to stabilize intermediate oxidation states or
mands of both academic and industrial sectors. Al- geometries during a catalytic cycle.[3] The most effi-
though the use of numerous chiral ligands has been cient of such ligands are P-mono, P,N- and P,P-biden-
reported, the design and synthesis of new types of li- tate compounds. Chelation is a general characteristic
gands with improved performance continue to attract of P,N- and P,P-ligands. As a rule, chelation reduces
the interest of synthetic chemists. A well-conceived the degree of rotational freedom around the metal-
ligand class should possess one or more structural phosphorus bond, leading to a certain degree of ri-
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gidity necessary for efficient transfer of chirality in
Note that the use of the phosphite-type ligands has
the catalytic process. Moreover, P,N-bidentate com- become an established tool in asymmetric catalysis.[4a]
pounds are able to generate electronic asymmetry on The most important advantages of such ligands in-
the metal. This asymmetry can be transmitted to re- clude their pronounced p-acidity, oxidation stability,
acting molecules bonded to the metal (for instance, as well as their synthetic availability and low cost.
through the trans-effect) and has the potential to con- This often enables ꢂfine-tuningꢃ towards desired prop-
trol both the stability and reactivity of metal-substrate erties, such as high selectivity and rate in homogene-
intermediates.[1–3] P-monodentate ligands represent a ous catalytic reactions.[5] Thus, P,P-bidentate phos-
class of widespread stereoselectors in asymmetric cat- phites LA–C were successfully used in the Cu-catalyzed
alysis, and their coordination mode allows the devel- conjugated addition, Co-catalyzed Pauson–Khand re-
opment of new strategies in combinatorial asymmetric action and Rh-catalyzed hydroformylation,[6–8] but
catalysis, which are impossible with bidentate li- phosphites LD–F containing phosphocycles based on
gands.[4]
chiral aliphatic diols appeared to be rather ineffective
To embark on the synthesis of any modern ligands, stereoselectors.[9] NOBIN-based P,N-bidentate phos-
it is necessary to select carefully the optimal back- phites LG,H are highly efficient in the Cu-catalyzed
bone. Ligands embodying the binaphthyl framework enantioselective conjugate additions, and P-monoden-
have earned a prominent status as shown by their ver- tate MOP-type compounds LI,J were shown to have
satility in many catalytic asymmetric reactions over good to excellent enantioselectivity in the Pd-cata-
the last three decades.[1,2a] Standard BINOL-derived lyzed allylation and in the Rh-catalyzed hydrogena-
monophosphites[4a] and monophosphoramidites[4b] are tion.[10,11]
considered to be priviledged ligands. However, struc-
In the last few years, we have developed a new
tural variations lead to further interesting perspec- class of highly modular diamidophosphite ligands
tives. Examples of some phosphite-type compounds with 1,3,2-diazaphospholidine rings that promote a
with different coordination modes and binaphthyl wide range of catalytic asymmetric reactions.[12] It
backbone are shown in Figure 1.
should be noted that these P*-chiral 1,3,2-diazaphos-
Figure 1. P-Mono-, P,N- and P,P-bidentate phosphite-type ligands for asymmetric metal complex catalysis.
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Asymmetric Catalytic Reactions Using P*-Mono-, P*,N- and P*,P*-Bidentate Diamidophosphites
pholidines belong to an attractive group of optically Results and Discussion
active diamidophosphite ligands. In particular, these
compounds display balanced electronic characteristics Ligand Design and Synthesis
since they are both good p-acceptors (due to the ac-
cessibility of low-lying p*PN orbitals) as well as good The general strategy for the synthesis of the starting
s-donors. The inclusion of the phosphorus atom in synthons 2 and 3 with the binaphthyl framework is
the five-membered ring enhances the resistance of the presented in Scheme 1.
ligands to oxidation and hydrolysis, and the possibility
Thus, (Sa)- and (Ra)-2-hydroxy-2’-tosyloxy-1,1’-bi-
of varying the nature of the substituents at the nitro- naphthyls (Sa)-2 and (Ra)-2 were conveniently ob-
gen and phosphorus atoms allows the control over the tained by direct interaction between the appropriate
steric and electronic parameters. Also, their modular enantiomer of BINOL and TsCl.[15] (Sa)- and (Ra)-
nature allows a facile systematic variation at the con- 2-hydroxy-2’-[(pyridin-2-yl)methoxy]-1,1’-binaphthyls
figuration of the P*- and C*-stereocenters in the (Sa)-3 and (Ra)-3 were easily synthesized according to
1,3,2-diazaphospholidine rings. As a whole, the stabili- a modified procedure from literature.[16]
ty of these ligands and their straightforward syntheses
provide easy fine tuning of their catalytic proper- efficiently by the one-step phosphorylation of BINOL
ties.[12,13]
1 or its derivatives 2 and 3 by reagent 4 in toluene
P*-Chiral diamidophosphites 5–7 were synthesized
As stated above, in enantioselective catalysis li- (Scheme 2). The reactions require the presence of
gands induce asymmetry in a reaction, not just Et3N as HCl scavenger. The target ligands 5–7 were
through steric factors, but also through the nature of obtained with overall yields ranging from 78% to
donor atoms and coordination mode. However, a sys- 89% after purification by chromatography on silica
tematic evaluation of the effectiveness of phosphite- gel (see Experimental Section).
type ligands within the framework of this concept is
All ligands are readily available and can be pre-
hampered by the lack of specially-designed series of pared on a gram scale. Furthermore, the phosphory-
them having the same backbone, but different donor lating agent 4 can easily be synthesized[12a] in high
atoms and denticity. In this connection, we report the yield from readily accessible (S)-glutamic acid ani-
synthesis of a small library of P*-mono, P*,N- and lide.[17] Moreover, BINOL 1 is commercially available
P*,P*-bidentate diamidophosphites 5–7 containing in both enantiomeric forms and is one of the cheapest
the (Sa)- or (Ra)-1,1’-binaphthyl core and 1,3,2-diaza- chiral auxiliaries currently on the market. As stated
phospholidine rings. We also present the results of above, its transformation into derivatives 2 and 3 re-
direct comparison of these stereoselectors in asym- quires only one or three simple steps, respectively.
metric catalysis.
The novel ligands are white solids, which are stable
Typically, once novel ligands have been prepared, enough to allow manipulation in open air and can be
their metal complexes are tested for their catalytic ac- stored under dry conditions at room temperature over
tivity and enantiodifferentiating ability in standard several months without any degradation. In addition,
transformations. These benchmark reactions include they are fairly stable in solutions in common organic
(among others) asymmetric hydrogenation and allylic solvents. They were fully characterized by 1H, 13C,
substitution. The enantioselective hydrogenation, and 31P NMR spectroscopy, EI and/or MALDI TOF/
using inexpensive molecular hydrogen and a small TOF mass spectrometry as well as by elemental anal-
amount of a catalyst, holds a considerable promise for ysis. These stereoselectors possess: (i) chirogenic
industrial use. The allylic substitution, which is toler- phosphorus donor atoms, (ii) a rigid structure imposed
ant to various functional groups in the substrate and by the atropoisomeric binaphthyl backbone and (iii)
operates with a wide range of C-, N-, O-, S-, and P- P*-mono, P*,N- and P*,P*-bidentate coordination
nucleophiles, has been successfully used in key steps modes. The 31P NMR spectroscopic data for diamido-
of the synthesis of various natural compounds.[14]
phosphites 5–7 are summarized in Table 1.
Scheme 1. Synthesis of BINOL-based compounds (Sa)-2, (Ra)-2 and (Sa)-3, (Ra)-3.
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Scheme 2. Synthesis of epimeric diamidophosphite ligands (Sa)-5, (Ra)-5; (Sa)-6, (Ra)-6 and (Sa)-7, (Ra)-7
Table 1. 31P NMR chemical shifts (CDCl3) and cone angles q
(deg.) of the phosphocenters of ligands (Sa)-5, (Ra)-5; (Sa)-6,
(Ra)-6 and (Sa)-7, (Ra)-7.
2
ized by large spin-spin coupling constants JC8“,P (33.4–
37.5 Hz, see Experimental Section), which are indica-
tive of the cis orientation of the phosphorus lone pair
with respect to the C-8” atom. Correspondingly, the
pseudoequatorially oriented exocyclic substituent at
Ligand
dP
q
(RP)-(Sa)-5 (91%)[a]
(SP)-(Sa)-5 (9%)
(RP)-(Ra)-5 (88%)
(SP)-(Ra)-5 (12%)
(RP)-(Sa)-6 (92%)
(SP)-(Sa)-6 (8%)
(RP)-(Ra)-6 (96%)
(SP)-(Ra)-6 (4%)
(Sa)-7
128.9
118.2
125.5
118.6
129.6
119.4
125.8
118.5
128.7
124.5
135
À
À
the phosphorus atom and the
pyrrolidine fragment of phosphabicyclic skeleton are
in the trans arrangement (Figure 2).
ACHTUGNTREN(UNNG CH2)3 part of the
129
128
133
On the contrary, the minor epimers of ligands 5
and 6 contain the asymmetric phosphorus atoms with
the (S) configuration.[11,12,17b,18]
In order to have an estimation of the steric de-
mands of diamidophosphites 5–7, we calculated their
Tolman cone angles[19] by the reported method using
a semi-empirical quantum-mechanical AM1 method
174[b]
168[b]
(Ra)-7
[a]
Percentage of P*-epimers.
The average value for both phosphocenters.
[b]
Compounds 5 and 6 are mixtures of epimers with
respect to the phosphorus stereocentre and contain
88-96% of the major P* epimers, while ligands 7 are
formed as single stereoisomers (Table 1). Ligands 7
and the major epimers of ligands 5, 6 have the P*
stereocentres with the (R) configuration. The
Figure 2. Stereochemistry of the phosphabicyclic part in li-
13C NMR spectra of these compounds are character- gands 7 and in major epimers of ligands 5, 6.
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Asymmetric Catalytic Reactions Using P*-Mono-, P*,N- and P*,P*-Bidentate Diamidophosphites
with full optimization of geometrical parameters.[20] ligand (Ra)-6 showed a considerably smaller enantio-
The obtained results showed that P*-mono, P*,N-bi- selectivity (Table 2, entries 7, 8). P*-Monodentate di-
dentate ligands 5 and 6 have moderate steric demands
ACHTUNGTRENNaGNU midophosphite (Sa)-5 afforded product (S)-9a with
and their steric parameters (q) vary within the narrow good enantiomeric purity (up to 86% ee), but the
interval of 1288–1358 (Table 1). In contrast, P*,P*-bi- analogous catalysts based on diastereomer (Ra)-5
dentate diamidophosphites (Sa)-7 and (Ra)-7 appear proved to be much less efficient: only 58% yield and
to be rather bulky ligands (q=1748 and 1688, respec- 30% ee for (S)-9a were achieved in this case (Table 2,
tively).[19,21]
entries 1–4). P*,P*-Bidentate ligands 7 are mediocre
stereoselectors: enantioselectivity varies from 30% to
67% ee (Table 2, entries 9–12).
Palladium- and Platinum-Catalyzed Asymmetric
Allylic Substitution
In the next step, stereoselectors 5–7 were studied in
the Pd- and Pt-catalyzed asymmetric allylic alkylation
of substrate 8 (Table 3). In the Pd-catalyzed process,
Diamidophosphites 5–7 were first applied in the Pd- diamidophosphites 5–7 provided an excellent enantio-
catalyzed allylic sulfonylation of (E)-1,3-diphenylallyl selectivity irrespective of their denticity and absolute
acetate 8 with p-TolSO2Na as the S-nucleophile configuration of the binaphthyl backbone (95–99%
(Table 2).
ee, Table 3, entries 4, 7, 11, 13, 17 and 25). Like the
Compound 8 was chosen as a substrate because the Pd-catalyzed allylic sulfonylation, the experiments
reaction itself was performed with a wide range of li- with the use of ligands 5–7 afforded the reaction
gands, allowing the efficiency of the various ligand product 9b having the (S) configuration. In general,
systems to be compared directly.[1b,d,14e] In all cases, 5– both the conversion of 8 and asymmetric induction
7 provided the formation of the (S)-enantiomer of were poorly sensitive to the L/Pd molar ratio and sol-
sulfone 9a. P*,N*-bidentate ligand (Sa)-6 was the vent nature. Nevertheless, it is possible to specify
most efficient, and (S)-9a was formed with 89% yield some correlations. In particular, for P*-monodentate
and 99% ee (Table 2, entry 5). It should be noted that diamidophosphites 5 the molar ratio L/Pd=2 is un-
chiral allylic sulfones are exceptionally versatile inter- doubtedly preferable (Table 3, entries 1–8). In most
mediates in organic synthesis.[14c] Diastereomeric cases, with participation of P*-mono- and P*,N-biden-
tate ligands 5 and 6, the higher enantioselectivity was
observed in CH2Cl2, with participation of P*,P*-bi-
dentate ligands 7 – in THF. In the presence of
[PtACTHNUTRGNEG(NU allyl)Cl]4 as the metal precursor, diamidophos-
Table 2. Pd-catalyzed allylic sulfonylation of (E)-1,3-diphe-
nylallyl acetate 8 with sodium para-toluenesulfinate.[a]
phite (Sa)-7 provided a somewhat lower enantioselec-
tivity (ee is no higher than 87%) (Table 3, entries 21–
24), but it was comparable to that of the effective
P,N- and P,P-bidentate phosphine stereoselectors
PHOX and CHIRAPHOS.[22] It should be noted that
the Pt-catalyzed alkylation of substrate 8 with partici-
pation of (Sa)-7 resulted in higher conversion and
enantioselectivity in CH2Cl2, and the resulting product
9b also showed the (R) configuration. At the same
time, diastereomeric ligand (Ra)-7 afforded product
(S)-9b with lower enantiomeric purity (up to 76% ee,
Table 3, entries 29, 30).
Ligands 5–7 were next evaluated in the Pd-cata-
lyzed allylic amination of (E)-1,3-diphenylallyl acetate
8 with dipropylamine as an N-nucleophile. As in the
case of the allylic sulfonylation, positive influence on
the enantioselectivity was observed for P*,N-biden-
tate coordination mode, (+)-9c was obtained in 90%
and 98% ee with (Sa)-6 and (Ra)-6, respectively
(Table 4, entries 10 and 13).
Entry
Ligand
L/Pd
Yield [%]
ee[b] [%]
1
2
3
4
5
6
7
8
(Sa)-5
(Sa)-5
(Ra)-5
(Ra)-5
(Sa)-6
(Sa)-6
(Ra)-6
(Ra)-6
(Sa)-7
(Sa)-7
(Ra)-7
(Ra)-7
1/1
2/1
1/1
2/1
1/1
2/1
1/1
2/1
1/1
2/1
1/1
2/1
88
47
49
58
89
67
62
90
63
90
40
53
86 (S)
77 (S)
30 (S)
5 (S)
99 (S)
97 (S)
86 (S)
75 (S)
55 (S)
30 (S)
67 (S)
59 (S)
9
10
11
12
For comparison, the corresponding ligands with a
different denticity (5 and 7, Scheme 2) afforded the
amination product (+)-9c with 84% and 89% ee, re-
spectively. As clearly shown in Table 4, very high
enantioselectivity was observed for both diastereo-
mers of P*,N-bidentate diamidophosphite 6 (en-
[a]
All reactions were carried out with 2 mol% of
[Pd(allyl)Cl]2 in THF at room temperature for 48 h.
Enantiomeric excess of 9a was determined by HPLC
(Daicel Chiralcel OJ, C6H14/i-PrOH=4/1, 0.5 mLminÀ1,
254 nm).
ACHTUNGTRENNUNG
[b]
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Konstantin N. Gavrilov et al.
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Table 3. Pd- and Pt-catalyzed allylic alkylation of (E)-1,3-di-
phenylallyl acetate 8 with dimethyl malonate.[a]
Table 4. Pd-catalyzed allylic amination of (E)-1,3-diphenyl-
allyl acetate 8 with dipropylamine.[a]
Entry Ligand L/Pd or L/
Pt
Solvent Conv.[b]
[%]
ee[b]
[%]
Entry Ligand L/Pd Solvent Conv.[b] [%] ee[b] [%]
1
2
3
4
5
6
7
8
(Sa)-5 1/1
(Sa)-5 2/1
(Sa)-5 1/1
(Sa)-5 2/1
(Ra)-5 1/1
(Ra)-5 2/1
(Ra)-5 1/1
(Ra)-5 2/1
(Sa)-6 1/1
(Sa)-6 2/1
(Sa)-6 1/1
(Sa)-6 2/1
(Ra)-6 1/1
(Ra)-6 2/1
(Ra)-6 1/1
(Ra)-6 2/1
(Sa)-7 1/1
(Sa)-7 2/1
(Sa)-7 1/1
(Sa)-7 2/1
(Sa)-7 1/1
(Sa)-7 2/1
(Sa)-7 1/1
(Sa)-7 2/1
(Ra)-7 1/1
(Ra)-7 2/1
(Ra)-7 1/1
(Ra)-7 2/1
(Ra)-7 1/1
(Ra)-7 2/1
THF
THF
23
58
51 (S)
87 (S)
92 (S)
96 (S)
55 (S)
97 (S)
98 (S)
97 (S)
92 (S)
94 (S)
95 (S)
88 (S)
97 (S)
72 (S)
95 (S)
97 (S)
99 (S)
92 (S)
94 (S)
65 (S)
60 (R)[c]
72 (R)[c]
87 (R)[c]
85 (R)[c]
98 (S)
93 (S)
73 (S)
95 (S)
76 (S)[c]
59 (S)[c]
1
2
3
4
5
6
7
8
(Sa)-5
(Sa)-5
(Sa)-5
(Sa)-5
(Ra)-5
(Ra)-5
(Ra)-5
(Ra)-5
(Sa)-6
(Sa)-6
(Sa)-6
(Sa)-6
(Ra)-6
(Ra)-6
(Ra)-6
(Ra)-6
(Sa)-7
(Sa)-7
(Sa)-7
(Sa)-7
(Ra)-7
(Ra)-7
(Ra)-7
(Ra)-7
1/1
2/1
1/1
2/1
1/1
2/1
1/1
2/1
1/1
2/1
1/1
2/1
1/1
2/1
1/1
2/1
1/1
2/1
1/1
2/1
1/1
2/1
1/1
2/1
THF
THF
CH2Cl2 100
CH2Cl2 100
THF
THF
CH2Cl2 64
CH2Cl2 70
THF
THF
CH2Cl2 72
CH2Cl2 100
THF
THF
CH2Cl2 96
CH2Cl2 100
THF
THF
CH2Cl2 100
CH2Cl2 100
THF
THF
100
97
80 (+)
84 (+)
67 (+)
57 (+)
15 (+)
20 (+)
20 (+)
25 (+)
89 (+)
90 (+)
88 (+)
88 (+)
98 (+)
90 (+)
80 (+)
87 (+)
4 (À)
CH2Cl2 78
CH2Cl2 100
THF
THF
91
99
25
46
CH2Cl2 67
CH2Cl2 96
9
THF
THF
52
66
9
32
20
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
CH2Cl2 99
CH2Cl2 99
THF
THF
85
45
71
31
CH2Cl2 38
CH2Cl2 72
THF
THF
57
65
38
37
2 (À)
CH2Cl2 94
CH2Cl2 93
19 (À)
34 (À)
88 (+)
89 (+)
65 (+)
53 (+)
THF
THF
56
54
50
58
CH2Cl2 73
CH2Cl2 61
CH2Cl2 91
CH2Cl2 100
THF
THF
59
57
[a]
All reactions were carried out with 2 mol% of
[Pd(allyl)Cl]2 at room temperature for 48 h.
Both the conversion of substrate 8 and enantiomeric
excess of 9c were determined by HPLC [Daicel Chiralcel
OD-H, C6H14/i-PrOH/HNEt2 =1000/1/1, 0.4 mLminÀ1,
254 nm, t(+)=8.2 min, t(À)=9.1 min].
CH2Cl2 46
CH2Cl2 56
CH2Cl2 98
CH2Cl2 99
AHCTUNGTRENNUNG
[b]
[a]
[b]
[c]
All reactions were carried out with 2 mol% of
[Pd(allyl)Cl]2 or 1 mol% [Pt(allyl)Cl]4 at room tempera-
ture for 48 h (BSA, KOAc).
Both the conversion of substrate 8 and enantiomeric
excess of 9b were determined by HPLC (Daicel Chiral-
cel OD-H, C6H14/i-PrOH=99/1, 0.6 mLminÀ1, 254 nm).
G
ACHTUNGTRENNUNG
cant effect on the reaction rate or asymmetric induc-
tion (Table 4, entries 9–16).
Table 5 shows the results obtained when pyrrolidine
was used as an alternative N-nucleophile. Catalytic
performance in the Pd-catalyzed allylic amination of
8 with pyrrolidine followed the same trend as for the
With [PtACHTUNGTRENNUNG(allyl)Cl]4 as a precatalyst.
tries 9–16), while efficiency of P*-monodentate (Sa)-5 allylic alkylation of 8. From good to excellent enan-
and (Ra)-5 was quite different (entries 1–4 and 5–8). tioselectivity (81–99% ee) was observed when em-
Similarly, P*,P*-bidentate (Ra)-7 is a rather good ster- ploying diamidophosphites 5–7 with different coordi-
eoselector, but (Sa)-7 provided much lower asymmet- nation modes and absolute configuration of the bi-
ric induction. The reaction product (<M >)-9c also naphthyl backbone. The resulting product 9d proved
showed opposite absolute configuration (Table 4, en- to have the same (R) configuration in all cases. In
tries 17–24), probably due to the mismatched combi- contrast to the allylic amination of 8 with dipropyl-
nation of the (2’’R,5’’S)-stereocentres of the phospha-
ACHTUNGTRENUNaGN mine, diamidophosphite (Sa)-7 has been found to be
bicyclic cores with the (Sa)-BINOL framework. For an especially efficient stereoselector. This P*,P*-bi-
most efficient ligands 6, the nature of the solvent and dentate ligand gave amine (R)-9d with high enantio-
the L/Pd molar ratio were not found to have a signifi- meric purity (96–99% ee) (Table 5, entries 17–20) re-
2604
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Adv. Synth. Catal. 2010, 352, 2599 – 2610

Asymmetric Catalytic Reactions Using P*-Mono-, P*,N- and P*,P*-Bidentate Diamidophosphites
Table 5. Pd- and Pt-catalyzed allylic amination of (E)-1,3-di-
phenylallyl acetate 8 with pyrrolidine.[a]
ample of the use of organophosphorus ligands in the
Pt-catalyzed asymmetric allylic amination.[14e]
P*,P*-Bidentate diamidophosphites (Sa)-7 and (Ra)-
7 were also involved in the deracemization reaction
that provides valuable optically active allylic alcohols,
such as chalcol 11,[23] which is of considerable practi-
cal significance. Ethyl (E)-1,3-diphenylallyl carbonate
10 was chosen as a substrate (Table 6).
Entry Ligand L/Pd or L/
Pt
Solvent Conv.[b]
[%]
ee[b]
[%]
Table 6. Pd-catalyzed deracemization of ethyl (E)-1,3-diphe-
nylallyl carbonate 10.[a]
1
2
3
4
5
6
7
8
(Sa)-5 1/1
(Sa)-5 2/1
(Sa)-5 1/1
(Sa)-5 2/1
(Ra)-5 1/1
(Ra)-5 2/1
(Ra)-5 1/1
(Ra)-5 2/1
(Sa)-6 1/1
(Sa)-6 2/1
(Sa)-6 1/1
(Sa)-6 2/1
(Ra)-6 1/1
(Ra)-6 2/1
(Ra)-6 1/1
(Ra)-6 2/1
(Sa)-7 1/1
(Sa)-7 2/1
(Sa)-7 1/1
(Sa)-7 2/1
(Sa)-7 1/1
(Sa)-7 2/1
(Sa)-7 1/1
(Sa)-7 2/1
(Ra)-7 1/1
(Ra)-7 2/1
(Ra)-7 1/1
(Ra)-7 2/1
THF
THF
31
60
83 (R)
84 (R)
20 (R)
47 (R)
53 (R)
71 (R)
75 (R)
81 (R)
68 (R)
84 (R)
73 (R)
75 (R)
89 (R)
87 (R)
57 (R)
78 (R)
96 (R)
98 (R)
98 (R)
99 (R)
83 (S)[c]
50 (S)[c]
86 (S)[c]
84 (S)[c]
80 (R)
69 (R)
81 (R)
50 (R)
CH2Cl2 100
CH2Cl2 100
THF
THF
35
80
CH2Cl2 80
CH2Cl2 78
Conv.[b] [%]
ee[b] [%]
9
THF
THF
100
65
Entry
Ligand
L/Pd
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
1
2
3
4
(Sa)-7
(Sa)-7
(Ra)-7
(Ra)-7
1/1
2/1
1/1
2/1
65
90
56
93
90 (S)
86 (R)
87 (R)
29 (S)
CH2Cl2 99
CH2Cl2 100
THF
THF
63
65
CH2Cl2 100
CH2Cl2 100
[a]
All reactions were carried out with 2 mol% of
[Pd(allyl)Cl]2 in CH2Cl2 at room temperature for 48 h.
Both the conversion of substrate 10 and enantiomeric
excess of 11 were determined by HPLC (Daicel Chiralcel
OD-H, C6H14/i-PrOH=9/1, 0.7 mLminÀ1, 254 nm).
AHCTUNGTRENNUNG
THF
THF
48
68
[b]
CH2Cl2 100
CH2Cl2 90
THF
100
THF
100
CH2Cl2 100
CH2Cl2 100
Note that the complete conversion of a racemate to
one enantiomer without intermediate separation of
materials (deracemization) is one of the current chal-
lenges in asymmetric synthesis. Traditionally, the Pd-
catalyzed deracemization of allylic esters was carried
out in CH2Cl2-H2O (9:1) medium.[23] However, we
used a unique procedure carried out in anhydrous
CH2Cl2 with the formation of (Bu)4NHCO3 salt di-
rectly (in situ) in organic media.[11] Under these condi-
tions and at the molar ratio L/Pd=1, both ligands
(Sa)-7 and (Ra)-7 provided moderate conversion of 10,
and essentially equally good levels of asymmetric in-
duction (90% and 87% ee) with (S) and (R) configu-
ration of 11, respectively (Table 6, entries 1 and 3). It
is interesting, that the increase of the L/Pd molar
THF
THF
74
48
CH2Cl2 100
CH2Cl2 100
[a]
All reactions were carried out with 2 mol% of
[Pd(allyl)Cl]2 or 1 mol% [Pt(allyl)Cl]4 at room tempera-
ture for 48 h.
Both the conversion of substrate 8 and enantiomeric
excess of 9d were determined by HPLC (Daicel Chiralcel
OD-H, C6H14/i-PrOH/HNEt2 =200/1/0.1, 0.9 mLminÀ1,
254 nm).
G
ACHTUNGTRENNUNG
[b]
[c]
With [PtACHTUNGTRENNUNG(allyl)Cl]4 as a precatalyst
gardless of the L/Pd molar ratio and the nature of the ratio gave rise to product 11 having opposite absolute
solvent, and with the highest conversion being ob- configuration (Table 6, entries 1,2 and 3,4).
served in CH2Cl2. The Pt-catalyzed amination of (E)-
We also screened ligands 5–7 in the Pd-catalyzed al-
1,3-diphenylallyl acetate 8 with pyrrolidine was char- lylic alkylation of the cyclic substrate, cyclohex-2-enyl
acterized by the quantitative conversion of the start- ethyl carbonate 12, with dimethyl malonate as the C-
ing substrate and the good enantioselectivity of the nucleophile (Table 7). The enantioselectivity for the
resulting product (S)-9d, with opposite absolute con- cyclic substrate 12 is usually more difficult to control
figuration (up to 86% ee). The nature of the solvent than for the hindered acyclic substrate 8.[24] The ste-
did not influence the asymmetric induction, and the reochemistry of the alkylation of 12 revealed some re-
optimal L/Pt molar ratio is 1 (see Table 5, entries 21– markable trends. It is clear that P*-monodentate di-
24). To the best of our knowledge, this is the first ex-
ACHTUNGTRENaNUNG midophosphite (Sa)-5 demonstrated higher catalytic
Adv. Synth. Catal. 2010, 352, 2599 – 2610
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asc.wiley-vch.de
2605

Konstantin N. Gavrilov et al.
FULL PAPERS
Table 7. Pd-catalyzed allylic alkylation of cyclohex-2-enyl
ethyl carbonate 12 with dimethyl malonate.[a]
Rhodium-Catalyzed Asymmetric Hydrogenation
In this section, we report the use of the diamidophos-
phites 5–7 in the Rh-catalyzed enantioselective hydro-
genation of prochiral methyl esters of unsaturated
acids, viz., dimethyl itaconate 14a and methyl 2-acet-
amidoacrylate 14b (Table 8).
Table 8. Rh-catalyzed hydrogenation of a-dehydrocarboxylic
acid esters.[a]
Entry Ligand L/Pd Solvent Conv.[b] [%] ee[b] [%]
1
2
3
4
5
6
7
8
(Sa)-5
(Sa)-5
(Sa)-5
(Sa)-5
(Ra)-5
(Ra)-5
(Ra)-5
(Ra)-5
(Sa)-6
(Sa)-6
(Ra)-6
(Ra)-6
(Sa)-7
(Sa)-7
(Sa)-7
(Sa)-7
(Ra)-7
(Ra)-7
(Ra)-7
(Ra)-7
1/1
2/1
1/1
2/1
1/1
2/1
1/1
2/1
1/1
2/1
1/1
2/1
1/1
2/1
1/1
2/1
1/1
2/1
1/1
2/1
THF
THF
CH2Cl2 100
CH2Cl2 100
THF
THF
CH2Cl2 89
CH2Cl2 90
CH2Cl2 92
CH2Cl2 100
CH2Cl2 82
CH2Cl2 100
THF
THF
CH2Cl2 100
CH2Cl2 100
85
90
47 (R)
50 (R)
70 (R)
50 (R)
40 (R)
12 (R)
33 (R)
54 (R)
40 (R)
43 (R)
30 (R)
32 (R)
21 (S)
60 (S)
26 (S)
44 (S)
58 (R)
15 (R)
46 (R)
30 (R)
61
30
9
10
11
12
13
14
15
16
17
18
19
20
Entry Substrate Ligand L/Rh Conv.[b,c] [%] ee[b,c] [%]
1
2
3
4
5
6
7
8
14a
14a
14a
14a
14a
14a
14b
14b
14b
14b
14b
14b
(Sa)-5
(Ra)-5 2/1
(Sa)-6 1/1
(Ra)-6 1/1
2/1
70
100
20
100
100
100
100
100
100
35
60 (S)
45 (S)
0
4 (R)
>99 (R)
98 (R)
72 (R)
11 (R)
0
28
42
(Sa)-7
(Sa)-7
(Sa)-5
1/1
2/1
2/1
THF
THF
CH2Cl2 97
CH2Cl2 99
74
87
(Ra)-5 2/1
(Sa)-6 1/1
(Ra)-6 1/1
9
10
11
12
30 (S)
99 (S)
97 (S)
[a]
All reactions were carried out with 2 mol% of
[Pd(allyl)Cl]2 at room temperature for 48 h (BSA,
(Sa)-7
(Sa)-7
1/1
2/1
100
100
ACHTUNGTRENNUNG
KOAc).
[b]
[a]
Both the conversion of substrate 12 and enantiomeric
excess of 13 were determined by HPLC [Daicel Chiralcel
AD, C6H14/i-PrOH=200/1, 1 mLminÀ1, 219 nm, t(R)=
11.3 min, t(S)=12.1 min].
All reactions were carried out with 0.5 mol% of
[Rh(COD)2]BF4 in CH2Cl2 at 258C and 1.3 bar H2 for
AHCTUNGTRENNUNG
20 h.
[b]
Both the conversion of substrate 14a and enantiomeric
excess of 15a were determined by GC (Lipodex E,
25 mꢄ0.25 mm, 808C, 1 mLminÀ1) or HPLC [Daicel
Chiralcel OD-H, C6H14/i-PrOH=98/2, 0.8 mLminÀ1,
220 nm, t(R)=9.1 min, t(S)=16.1 min].
Both the conversion of substrate 14b and enantiomeric
excess of 15b were determined by GC [XE-valine(tert-
butylamide) 4ꢄ0.25 mm, 858C, 1 mLminÀ1].
activity and enantioselectivity (up to 70% ee) than its
diastereomer (Ra)-5 and bidentate ligands 6 and 7 (ee
is no higher than 54%, 43% and 60%, respectively;
Table 7, entries 1–4 and 5–20).
[c]
With the participation of diamidophosphites 5 and
6, (R)-enantiomer of product 13 is formed. At the
same time, like the Pd-catalyzed amination of 8 with
These benchmark substrates have been already in-
dipropylamine, the use of both isomers of ligand 7 vestigated with a wide variety of ligands characterized
made it possible to obtain product 13 with opposite by various donor groups.[1b,d] We can, therefore, com-
absolute configurations. (Table 7, entries 13–16 and pare directly the efficacy of different ligand systems.
17–20). In general, diamidophosphite (Sa)-5 showed In all cases, the catalysts were generated in situ from
enantioselectivities of up to 70% in the asymmetric the complex [RhACTHUNTRGNE(UNG COD)2]BF4 (COD is 1,5-cycloocta-
synthesis of dimethyl 2-(cyclohex-2-enyl)malonate 13, diene) and the corresponding ligand in CH2Cl2
which is a rather good result for the sterically unde- medium.
manding substrate 12 (see Ref.[24] and references cited
therein).
In the transformation of 14a to succinate (S)-15a, li-
gands 5 showed good conversion and mediocre enan-
tioselectivity (up to 60% ee, Table 8, entries 1 and 2).
Unfortunately, the use of both diastereomers of P*,N-
2606
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Adv. Synth. Catal. 2010, 352, 2599 – 2610

Asymmetric Catalytic Reactions Using P*-Mono-, P*,N- and P*,P*-Bidentate Diamidophosphites
bidentate diamidophosphite 6 generated an almost 225.5 Hz. As the 31P NMR data clearly showed the
racemic product 15a. On the contrary, P*,P*-biden- presence in solution of several Rh(I) catalytic precur-
tate ligand (Sa)-7 resulted in virtually quantitative sors based on (Ra)-5, it is possible to understand the
enantioselectivity (98 to >99% ee) regardless of the fact that this diamidophosphite is a less efficient ster-
L/Rh molar ratio. The asymmetric hydrogenation of eoselector than (Sa)-5 (Table 8, entries 1, 2 and 7, 8).
14b was characterized by similar trends. In particular, It should be further noted that in the case of the ex-
P*-monodentate diamidophosphites 5 allowed the cellent P*,P*-bidentate stereoselector (Sa)-7, only a
1
synthesis of product (R)-15b with moderate enantio- sharp doublet at dP =108.5, JP,Rh =227.2 Hz of the in-
selectivity, and (Sa)-5 was shown to be a better stereo- dividual cationic complex {RhACHTNUGTRNEUNG(COD)[(Sa)-7]}BF4 was
selector than its diastereomer (Ra)-5 (ee 72 and 11%, observed in the 31P NMR spectrum of the reaction so-
respectively, Table 8, entries 7 and 8). P*,N-Bidentate lution. At the same time, the situation with P*,N-bi-
diamidophosphites 6 were again practically inefficient dentate diamidophosphites 6 is rather ambiguous. On
(ee is no higher than 30%). As in the case of hydroge- the one hand, complex {RhACTHNUTRGEN(UNG COD)[(Ra)-6]}BF4
nation of dimethyl itaconate 14a, P*,P*-bidentate showed in the 31P NMR spectrum a broad signal with
ligand (Sa)-7 is an excellent stereoselector: the prod- maximum at 102.4 ppm and upfield shift relative to
uct (S)-15b was formed with the enantioselectivity up the free ligand. Such spectral behaviour can be ration-
to 99%.
In order to throw light on the nature of the catalyt- the eleven-membered P*,N-chelate ring. On the other
ic species, we carried out MALDI TOF/TOF and hand, the 31P NMR spectrum of [Rh
(COD)2]BF4/(Sa)-
31P NMR investigations of the rhodium complexes ob- 6 1:1 mixture contained two doublet signals of com-
alized by taking into account the flexible nature of
AHCTUNGTRENNUNG
tained from stereoselectors 5–7. The appropriate plexes {RhACTHNUGTRNEN(UG COD)[(SP)-(Sa)-6]2}BF4 at dP =111.6,
measurements were performed in dichloromethane 1JP,Rh =220.3 Hz (9%) and {Rh
(COD)[(RP)-(Sa)-
1
solutions of 1:2 mixtures of [Rh
mixtures of [Rh
G
A
drogenation reactions were carried out using these and (Ra)-6 were almost equally inefficient. Thus, the
ratios. It was shown that P*-monodentate diamido- reason behind this finding remains unclear. However,
phosphites 5 are capable of forming cationic com- there are some other examples of low conversion and/
plexes [RhACHTUNGTRENNUNG(COD)(5)2]BF4 bearing two phosphorus li- or asymmetric induction in the Rh-catalyzed hydroge-
gands which are cis-arranged at Rh(I). P*,N- and nation with participation of the BINOL-based P,N-bi-
P*,P*-bidentate ligands 6 and (Sa)-7 are chelating dentate ligands.[5d,25]
agents
and
form
cationic
metal
chelates
[Rh(COD)(6)]BF4 and {RhACHTGNUTRENNUNG
N
(COD)[(Sa)-7]}BF4 with
cis-orientation of the P*,N- or P*,P*- donor atoms. Conclusions
MALDI TOF/TOF mass spectral examination of the
resulting solutions revealed the mononuclear nature In summary, the present paper has led to the follow-
of the complexes {RhACHTUNGRTNEUNG(COD)[(Sa)-5]2}BF4 {m/z (I, ing conclusions: i) novel P*-chiral diamidophosphites
%)=1501
(18)
[MÀBF4]+,
1393
(100) 5–7 with 1,3,2-diazaphospholidine rings and (Sa)- or
[MÀBF4ÀCOD]+}, [Rh
ACHTUGNERTN(NUNG COD)(6)]BF4 {m/z (I, %)= (Ra)-binaphthyl backbone have been successfully syn-
793 (54) [MÀBF4]+, 685 (100) [MÀBF4ÀCOD]+) and thesized; ii) in asymmetric Pd-catalyzed allylation, P*-
{RhACHTUNGTRENNUNG(COD)[(Sa)-7]}BF4 {m/z (I, %)=906 (54) mono, P*,N- and P*,P*-bidentate diamidophosphites
[MÀBF4]+, 798 (100) [MÀBF4ÀCOD]+}. The are very efficient and complementary groups of ster-
31P NMR
[Rh
ence of a doublet signal of complex {Rh
(Sa)-5]2}BF4 based on major (RP)-(Sa)-5 P*-epimer at efficient stereoselectors than P*,P*-bidentate ligand
spectrum
of
the eoselectors; iii) in asymmetric Rh-catalyzed hydroge-
ACHTUNGTRENNUNG
AHCTUNGTRENNUNG
1
108.4 ppm with the typical coupling constant JP,Rh
=
(Sa)-7, whereas in Pd-catalyzed allylation they can
228.9 Hz (81%) and AX spin system of mixed com- demonstrate similar and even high productivity. The
plex {RhACHTUNGTRENNUNG(COD)[(RP)-(Sa)-5][(SP)-(Sa)-5]}BF4 dP = combination of high enantioselectivity (ees up to
105.9, 1JP,Rh =226.7 Hz, 2JP, P =38.2 Hz; dP =92.6, 99%), low cost, and easy synthesis of the ligands
2
1JP,Rh =227.4 Hz, JP, P =38.2 Hz (19%). In contrast, the makes them very attractive for further catalytic appli-
31P NMR
[Rh
spectrum
of
the cations. As a consequence, additional studies high-
ACHTUNGTRENNUNG(COD)2]BF4/(Ra)-5 1:2 mixture proved to be more lighting the potential of these new stereoselectors in
complicated and contained two dominant doublets other asymmetric reactions are now in progress in our
dP =107.2, 1JP,Rh =230.1 Hz (22%) and dP =101.9, laboratories.
1JP,Rh =213.8 Hz (53%) alongside with a number of
additional spectral signals in the interval 106.1–
97.6 ppm with coupling constants 1JP,Rh =188.3–
Adv. Synth. Catal. 2010, 352, 2599 – 2610
ꢁ 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
asc.wiley-vch.de
2607

Konstantin N. Gavrilov et al.
FULL PAPERS
2H), 7.13–7.26 (m, 6H), 7.47 (m, 1H), 7.72–7.91 (m, 4H),
Experimental Section
7.99 (m, 2H); 13C NMR (CDCl3): d=21.3 (s, CH3), 25.9 (d,
2
3J=4.2 Hz, C-7’’), 31.0 (s, C-6’’), 47.1 (d, J=33.4 Hz, C-8’’),
General Remarks
2
2
53.0 (d, J=7.3 Hz, C-4’’), 62.1 (d, J=8.4 Hz, C-5’’), 114.9
1
31P, 13C and H NMR spectra were recorded with a Bruker
(d, 3J=13.2 Hz, CHPh), 118.8 (s, CHPh), 121.1 (s, CHAr),
121.6 (s, CAr), 122.5 (d, J=7.0 Hz, CHAr), 123.7 (s, CHAr),
AMX 400 instrument (162.0 MHz for 31P, 100.6 MHz for 13C
and 400.13 MHz for 1H). Complete assignment of all the res-
onances in 13C NMR spectra was achieved by the use of
DEPT techniques. Chemical shifts (ppm) were given relative
to Me4Si (1H and 13C) and 85% H3PO4 (31P NMR). Mass
spectra were recorded with a Varian MAT 311 spectrometer
3
125.1 (s, CAr), 125.3 (s, CHAr), 125.8 (s, CHAr), 126.0 (s,
CHAr), 126.8 (s, CHAr), 127.0 (s, CHTs), 127.3 (s, CHAr), 127.7
(s, CHAr), 128.8 (s, CHPh), 129.0 (s, CHAr), 129.1 (s, CHTs),
129.7 (s, CAr), 130.1 (s, CHAr), 130.6 (s, CHAr), 131.4 (s, CAr),
133.5 (s, CAr), 133.7 (s, CAr), 143.7 (s, CTs), 144.6 (d, 2J=
15.7 Hz, CPh), 145.9 (s, CTs), 150.1 (s, CAr), 151.8 (d, 2J=
5.5 Hz, CAr); MS (EI): m/z (I, %)=645 (3) [M]+; MS
(MALDI TOF/TOF): m/z (I, %)=646 (10) [M+H]+, 491
(100) [MÀTs+H]+; anal. calcd. for C38H33N2O4PS: C 70.79,
H 5.16, N, 4.35; found: C 70.97, H 5.22, N 4.25.
(EI) and
a Bruker Daltonics Ultraflex spectrometer
(MALDI TOF/TOF). Elemental analyses were performed
at the Laboratory of Microanalysis (Institute of Organoele-
ment Compounds, Moscow).
All reactions were carried out under argon in freshly
dried and distilled solvents; Et3N, pyrrolidine and dipropyl-
amine were twice distilled over KOH and then over a small
amount of LiAlH4 before use. The phosphorylating reagent
2-[(2’’R,5’’S)-3’’-Phenyl-1’’,3’’-diaza-2’’-phosphabicyclo-
A
[(Ra)-5]:
1
White solid; yield: 2.58 g (80%); mp 109–1108C. H NMR
(CDCl3): d=1.40 (m, J=11.5 Hz, 2H), 1.66 (m, J=11.5 Hz,
2H), 2.25 (s, 3H), 2.95 (m, J=7.2, 6.6 Hz, 2H), 3.1 (m, 1H),
3.37 (m, 2H), 6.64 (d, J=9.0 Hz, 2H), 6.83 (d, J=9.0 Hz,
1H), 6.92 (m, 3H), 7.05 (d, J=8.9 Hz, 2H), 7.12–7.26 (m,
6H), 7.44 (m, 1H), 7.72–7.93 (m, 4H), 8.03 (m, 2H);
–
(5S)-2-chloro-3-phenyl-1,3-diaza-2-phosphabicyclo
octane 4 – was prepared as published.[12a] [Pd
(allyl)Cl]2,
[Pt(allyl)Cl]4 and [Rh(COD)2]BF4 were prepared as de-
ACHTUNGTRENN[UNG 3.3.0]-
AHCTUNGTRENNUNG
N
ACHTUNGTRENNUNG
scribed earlier.[26–28] Starting substrates (E)-1,3-diphenylallyl
acetate 8, ethyl (E)-1,3-diphenylallyl carbonate 10 and cy-
clohex-2-enyl ethyl carbonate 12 were synthesized as pub-
lished.[26,29,30] (Sa)- and (Ra)-2,2’-dihydroxy-1,1’-binaphthyls
(Sa)-1 and (Ra)-1, sodium para-toluenesulfinate, dimethyl
malonate, BSA [N,O-bis(trimethylsilyl)acetamide] and start-
ing substrates dimethyl itaconate 14a and methyl 2-acetami-
doacrylate 14b were purchased from Aldrich and Acros Or-
ganics and used without further purification.
3
13C NMR (CDCl3): d=21.1 (s, CH3), 26.1 (d, J=4.2 Hz, C-
2
2
7’’), 31.1 (s, C-6’’), 47.5 (d, J=35.4 Hz, C-8’’), 53.4 (d, J=
7.1 Hz, C-4’’), 63.0 (d, 2J=8.2 Hz, C-5’’), 115.1 (d, 3J=
13.2 Hz, CHPh), 118.9 (s, CHPh), 121.1 (s, CHAr), 122.8 (s,
3
CAr), 123.1 (d, J=7.3 Hz, CHAr), 123.4 (s, CHAr), 125.1 (s,
CAr), 125.5 (s, CHAr), 125.7 (s, CHAr), 126.1 (s, CHAr), 126.5
(s, CHAr), 127.0 (s, CHTs), 127.2 (s, CHAr), 127.9 (s, CHAr),
128.7 (s, CHPh), 129.0 (s, CHAr), 129.3 (s, CHTs), 129.8 (s,
CAr), 130.4 (s, CHAr), 130.9 (s, CHAr), 131.4 (s, CAr), 133.2 (s,
For Pd- and Pt-catalyzed allylic substitution reactions, sul-
fonylation of substrate 8 with sodium para-toluenesulfinate,
alkylation with dimethyl malonate, amination with dipropyl-
amine and pyrrolidine; and alkylation of substrate 12 with
dimethyl malonate were performed according to the appro-
priate procedures.[12a,b,31,32,12c] Pd-catalyzed deracemization of
substrate 10 was performed according to the known proce-
dure.[11] Rh-catalyzed hydrogenation of a-dehydrocarboxylic
acid esters 14a, b was performed as published.[12c,33]
2
CAr), 133.7 (s, CAr), 143.8 (s, CTs), 144.3 (d, J=16.1 Hz, CPh),
2
146.3 (s, CTs), 150.0 (s, CAr), 153.5 (d, J=5.2 Hz, CAr); MS
(MALDI TOF/TOF): m/z (I, %)=646 (21) [M+H]+, 491
(100) [MÀTs+H]+; anal. calcd. for C38H33N2O4PS: C 70.79,
H 5.16, N, 4.35; found: C 70.91, H 5.02, N 4.41.
2-[(2’’R,5’’S)-3’’-Phenyl-1’’,3’’-diaza-2’’-phosphabicyclo-
AHCTUNGERTG[NNUN 3.3.0]octyloxy]-2’-[(pyridin-2-yl)methoxy]-(Sa)-1,1’-bi-
naphthyl [(Sa)-6]: White solid; yield: 2.38 g (82%); mp 84–
1
858C. H NMR (CDCl3): d=1.38 (m, J=11.2 Hz, 1H), 1.53
General Procedure for the Synthesis of Ligands (Sa)-
5, (Ra)-5 and (Sa)-6, (Ra)-6
(m, J=11.2 Hz, 3H), 2.60 (m, J=7.5, 6.4 Hz, 1H), 2.88 (m,
1H), 2.98 (m, 1H), 3.29 (m, 2H), 5.23 (s, 2H), 6.65 (d, J=
6.1 Hz, 2H), 6.83 (m 2H), 7.09 (m, 3H), 7.19 (m, 2H), 7.25
(m, 2H), 7.35–7.46 (m, 4H), 7.51 (d, J=9.0 Hz, 1H), 7.88
(d, J=9.0 Hz, 1H), 7.95 (m, 3H), 8.48 (m, 1H); 13C NMR
A solution of compounds 2 or 3 (5 mmol) in toluene
(15 mL) was added dropwise to a vigorously stirred solution
of phosphorylating reagent 4 (1.21 g, 5 mmol) and Et3N
(0.73 mL, 5.2 mmol) in toluene (15 mL). The mixture was
then heated to the boiling point, stirred for 15 min and
cooled to 208C. Solid Et3N·HCl was filtered off; toluene
was removed under reduced pressure (40 Torr). Products
(Sa)-5, (Ra)-5 and (Sa)-6, (Ra)-6 were purified by flash chro-
matography on silica gel using undegassed eluents (EtOAc/
hexane 1/2 and 1/1, respectively) and dried in vacuum (1
Torr) for 2 h.
3
(CDCl3): d=25.8 (d, J=3.7 Hz, C-7’’), 30.7 (s, C-6’’), 47.2
(d, 2J=33.5 Hz, C-8’’), 53.3 (d, 2J=6.9 Hz, C-4’’), 61.9 (d,
2J=8.4 Hz, C-5’’), 70.0 (s, OCH2), 114.2 (s, CHPy), 114.7 (d,
3J=12.8 Hz, CHPh), 118.7 (s, CHPh), 119.9 (s, CAr), 120.8 (s,
3
CHAr), 121.8 (s, CHAr), 122.9 (d, J=6.6 Hz, CHAr), 123.3 (s,
3
CHAr), 124.0 (s, CHAr), 124.3 (d, J=2.9 Hz, CAr), 125.8 (s,
CHAr), 125.9 (s, CHAr), 127.5 (s, CHAr), 127.7 (s, CHAr),
127.5 (s, CHAr), 127.7 (s, CHAr), 128.6 (s, CHPh), 128.7 (s,
CHPy), 128.9 (s, CAr), 129.8 (s, CHAr), 130.2 (s, CAr), 133.9 (s,
2-[(2’’R,5’’S)-3’’-Phenyl-1’’,3’’-diaza-2’’-phosphabicyclo-
2
CAr), 134.1 (s, CAr), 136.3 (s, CHPy), 144.8 (d, J=15.7 Hz,
[3.3.0]octyloxy]-2’-tosyloxy-(Sa)-1,1’-binaphthyl
[(Sa)-5]:
1
CPh), 148.2 (s, CHPy), 149.7 (s, CAr), 153.7 (s, CAr), 157.6 (s,
CPy); MS (EI): m/z (I, %)=582 (2) [M]+; MS (MALDI
TOF/TOF): m/z (I, %)=583 (15) [M+H]+, 475 (100)
[MÀOCH2Py+H]+; anal. calcd. for C37H32N3O2P: C 76.40,
H 5.55, N, 7.22; found: C 76.67, H 5.60, N 7.04.
White solid; yield: 2.51 g (78%); mp 149–1508C. H NMR
(CDCl3): d=1.33 (dq, J=11.4 Hz, 1H), 1.43 (m, 2H), 1.65
(dq, J=11.4 Hz, 1H), 2.21 (s, 3H), 2.94 (m, J=7.3, 6.6 Hz,
2H), 3.08 (m, 1H), 3.35 (m, 2H), 6.65 (d, J=9.1 Hz, 2H),
6.83 (d, J=9.1 Hz, 1H), 6.94 (m, 3H), 7.04 (d, J=8.9 Hz,
2608
asc.wiley-vch.de
ꢁ 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Adv. Synth. Catal. 2010, 352, 2599 – 2610

Asymmetric Catalytic Reactions Using P*-Mono-, P*,N- and P*,P*-Bidentate Diamidophosphites
2-{(2’’R,5’’S)-3’’-phenyl-1’’,3’’-diaza-2’’-phosphabicyclo-
(m, 4H), 3.4 (m, 4H), 6.65 (d, J=7.7 Hz, 4H), 6.70 (t, J=
U
8.0 Hz, 4H), 7.05 (t, J=8.4 Hz, 4H), 7.16 (m, 4H), 7.33 (d,
J=7.8, 7.1 Hz, 2H), 7.75 (d, J=8.3 Hz, 4H); 13C NMR
1
3
918C. H NMR (CDCl3): d=1.39 (m, J=11.4 Hz, 1H), 1.56
(CDCl3): d=25.9 (d, J=4.4 Hz, C-7’’), 31.1 (s, C-6’’), 47.1
(m, J=11.4 Hz, 3H), 2.63 (m, J=7.5, 6.5 Hz, 1H), 2.88 (m,
1H), 3.0 (m, 1H), 3.31 (m, 2H), 5.21 (s, 2H), 6.66 (d, J=
7.3 Hz, 2H), 6.83 (m 2H), 7.11 (m, 3H), 7.17 (m, 2H), 7.24
(m, 2H), 7.35–7.44 (m, 4H), 7.52 (d, J=8.8 Hz, 1H), 7.88
(d, J=8.8 Hz, 1H), 7.93 (m, 3H), 8.51 (m, 1H); 13C NMR
(d, 2J=37.5 Hz, C-8’’), 53.6 (d, 2J=8.2 Hz, C-4’’), 62.6 (d,
2J=8.9 Hz, C-5’’), 115.1 (d, 3J=12.3 Hz, CHPh), 118.7 (s,
3
CHPh), 123.1 (d, J=5.2 Hz, CHAr), 123.5 (s, CHAr), 124.5 (s,
CAr), 125.1 (s, CHAr), 127.0 (s, CHAr), 127.8 (s, CHAr), 128.6
(s, CHAr), 128.9 (s, CHPh), 130.1 (s, CAr), 134.3 (s, CAr), 145.4
(d, 2J=16.1 Hz, CPh), 150.3 (d, 2J=8.1 Hz, CAr); MS
(MALDI TOF/TOF): m/z (I, %)=718 (100) [M+Na]+, 696
(54) [M+H]+; anal. calcd. for C42H40N4O2P2: C 72.61, H
5.80, N, 8.06; found: C 72.91, H 5.92, N 8.23.
3
(CDCl3): d=25.8 (d, J=4.0 Hz, C-7’’), 31.2 (s, C-6’’), 47.2
(d, 2J=35.4 Hz, C-8’’), 53.7 (d, 2J=7.3 Hz, C-4’’), 62.3 (d,
2J=8.8 Hz, C-5’’), 71.3 (s, OCH2), 114.7 (d, 3J=13.1 Hz,
CHPh), 114.8 (s, CHPy), 118.8 (s, CHPh), 119.9 (s, CAr), 121.0
3
(s, CHAr), 121.9 (s, CHAr), 122.8 (d, J=5.5 Hz, CHAr), 123.3
3
(s, CHAr), 124.1 (s, CHAr), 124.2 (d, J=2.9 Hz, CAr), 125.8
(s, CHAr), 125.9 (s, CHAr), 126.0 (s, CHAr), 126.1 (s, CHAr),
127.6 (s, CHAr), 127.7 (s, CHAr), 128.7 (s, CHPh), 128.8 (s,
CHPy), 129.1 (s, CAr), 129.3 (s, CHAr), 130.3 (s, CAr), 133.9 (s,
Acknowledgements
2
We acknowledge the financial support by the Russian Foun-
dation for Basic Research (Grant No. 08-03-00416-a) and a
grant from the President of the Russian Federation for Young
Candidates of Sciences (No. MK-3889.2010.3). M.G.M.
thanks the DAAD Foundation for a research fellowship.
CAr), 134.0 (s, CAr), 136.3 (s, CHPy), 145.0 (d, J=16.4 Hz,
CPh), 148.3 (s, CHPy), 150.0 (d, 2J=6.2 Hz, CAr), 153.9 (s,
CAr), 157.8 (s, CPy); MS (MALDI TOF/TOF): m/z (I, %)=
583 (11) [M+H]+, 475 (100) [MÀOCH2Py+H]+; anal.
calcd. for C37H32N3O2P: C 76.40, H 5.55, N, 7.22; found: C
76.22, H 5.67, N 7.26.
References
General Procedure for the Synthesis of Ligands (Sa)-
7, (Ra)-7
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A solution of compound 1 (1.43 g, 5 mmol) in toluene
(17 mL) was added dropwise to a vigorously stirred solution
of phosphorylating reagent 4 (2.41 g, 10 mmol) and Et3N
(1.45 mL, 10.4 mmol) in toluene (26 mL) within 30 min. The
reaction mixture was stirred 24 h at room temperature. Solid
Et3N·HCl was filtered off; toluene was removed under re-
duced pressure (40 Torr). Products (Sa)-7, (Ra)-7 were puri-
fied by column chromatography on silica gel using unde-
gassed eluents (EtOAc/hexane 1/1) and dried in vacuum (1
Torr) for 2 h.
2,2’-Bis{(2’’R,5’’S)-3’’-phenyl-1’’,3’’-diaza-2’’-phospha-
bicycloACHTUNGTRENNUNG[3.3.0]octyloxy}-(Sa)-1,1’-binaphthyl [(Sa)-7]: White
solid; yield: 2.92 g (84%); mp 144–1458C. 1H NMR
(CDCl3): d=1.37 (dq, J=11.8 Hz, 2H), 1.5 (m, 4H), 1.68
(dq, J=11.8 Hz, 2H), 2.53 (ddd, J=8.2, 7.1, 5.9 Hz, 2H), 2.9
(m, 4H), 3.4 (m, 4H), 6.65 (d, J=7.8 Hz, 4H), 6.71 (t, J=
7.9 Hz, 4H), 7.02 (t, J=8.5 Hz, 4H), 7.16 (m, 4H), 7.36 (d,
J=7.7, 7.3 Hz, 2H), 7.74 (d, J=8.3 Hz, 4H); 13C NMR
3
(CDCl3): d=25.6 (d, J=4.4 Hz, C-7’’), 31.3 (s, C-6’’), 47.1
(d, 2J=36.5 Hz, C-8’’), 53.8 (d, 2J=8.0 Hz, C-4’’), 62.3 (d,
2J=8.8 Hz, C-5’’), 114.9 (d, 3J=12.4 Hz, CHPh), 118.7 (s,
3
CHPh), 123.1 (d, J=5.1 Hz, CHAr), 123.6 (s, CHAr), 124.5 (s,
CAr), 125.3 (s, CHAr), 127.0 (s, CHAr), 127.6 (s, CHAr), 128.4
(s, CHAr), 128.8 (s, CHPh), 130.1 (s, CAr), 134.1 (s, CAr), 145.2
(d, 2J=16.1 Hz, CPh), 150.1 (d, 2J=8.0 Hz, CAr); MS (EI):
m/z (I, %)=695 (2) [M]+; MS (MALDI TOF/TOF): m/z (I,
%)=718 (100) [M+Na]+, 696 (28) [M+H]+; anal. calcd. for
C42H40N4O2P2: C 72.61, H 5.80, N, 8.06; found: C 72.88, H
5.86, N 7.93.
2,2’-Bis{(2’’R,5’’S)-3’’-phenyl-1’’,3’’-diaza-2’’-phospha-
bicycloACHTUNGTRENNUNG[3.3.0]octyloxy}-(Ra)-1,1’-binaphthyl [(Ra)-7]: White
solid; yield: 3.09 g (89%); mp 126–1278C. 1H NMR
(CDCl3): d=1.35 (dq, J=11.8 Hz, 2H), 1.5 (m, 4H), 1.69
(dq, J=11.8 Hz, 2H), 2.55 (ddd, J=8.1, 7.2, 6.0 Hz, 2H), 3.0
Adv. Synth. Catal. 2010, 352, 2599 – 2610
ꢁ 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
asc.wiley-vch.de
2609

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ꢁ 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Adv. Synth. Catal. 2010, 352, 2599 – 2610