MOP-type binaphthyl phosphite and diamidophosphite ligands and their application in catalytic asymmetric transformations

Article abstract of DOI:10.1002/adsc.200600340

Monodentate phosphite and diamidophosphite ligands have been developed based on O-methyl-BINOL. These chiral ligands are easy to prepare from readily accessible phosphorylating reagents - (S_a or R_a)-2- chlorodinaphtho[2,1-d:1′,2′-f]-

Full text of DOI:10.1002/adsc.200600340

FULL PAPERS
DOI: 10.1002/adsc.200600340
MOP-Type Binaphthyl Phosphite and Diamidophosphite Ligands
and Their Application in Catalytic Asymmetric Transformations
Konstantin N. Gavrilov,a Sergey E. Lyubimov,b,* Sergey V. Zheglov,a
Eduard B. Benetsky,b Pavel V. Petrovskii,b Eugenie A. Rastorguev,a
Tatiana B. Grishina,a and Vadim A. Davankovb
a
Department of Chemistry, Ryazan State University, 46 Svoboda str., Ryazan 390000, Russia
Fax : (+7)-0912-775-498
b
Institute of Organoelement Compounds, Russian Academy of Sciences, 28 Vavilova str., Moscow 119991, Russia
Fax : (+7)-095-135-6471; e-mail: lssp452@mail.ru
Received: July 11, 2006; Revised: February 6, 2007
Abstract: Monodentate phosphite and diamidophos- dine (up to 97% ee), dipropylamine (up to 95% ee)
phite ligands have been developed based on O- and dimethyl malonate (up to 99% ee). In the palla-
methyl-BINOL. These chiral ligands are easy to pre- dium-catalysed deracemization of ethyl (E)-1,3-di-
pare from readily accessible phosphorylating re- phenylallyl carbonate, up to 96% enantioselectivity
agents – (Sa or Ra)-2-chlorodinaphtho[2,1-d:1’,2’-f]- has been achieved. The diamidophosphite ligands
ACHTREUNG
AHCTREUNG
new ligands have demonstrated excellent enantiose- itaconate (up to 90% ee).
lectivity in the palladium-catalysed allylic substitu-
tion reactions of (E)-1,3-diphenylallyl acetate with Keywords: allylic substitution; asymmetric catalysis;
sodium p-toluenesulfinate (up to 99% ee), pyrroli- hydrogenation; P ligands
Introduction
enantioselective allylic transformations. In the stan-
dard benchmark test, namely allylic alkylation of (E)-
In the last few years significant achievements have 1,3-diphenylallyl acetate with dimethyl malonate, they
taken place in the application of chiral P monoden- afforded up to 97% (La), 93% (Lb), 95% (Lc) and
tate phosphite-type ligands for asymmetric reactions. 77% ee (Ld).[21–24] Other Pd-catalysed reactions with
Such compounds showed excellent results in enantio- chiral monodentate phosphites have been explored
selective rhodium-catalysed hydrogenation and addi- fragmentarily. For example, the palladium complex of
tion of arylboronic acids, copper-catalysed addition of Le promotes the key step of enantioselective synthesis
organozinc and organoaluminium reagents, iridium- of alkaloid (+)-g-lycorane.[19,25]
catalysed allylic substitution, palladium-catalysed hy-
We describe here the applications of the novel
drosilylation-oxidation
and
diboration-allylation, phosphite and diamidophosphite analogues of the
nickel-catalysed hydrovinylation and cycloisomerisa- well-known phosphine MOP[26,27] (Figure 2) in various
tion, ruthenium-catalysed hydrogenation of ketones asymmetric transformations, first of all to Pd-cata-
and cyclopropanation.[1–18] Nevertheless, the number lysed allylation and to Rh-catalysed hydrogenation.
of chiral P monodentate phosphites that have been
It is of note that, in comparison with traditional
studied in Pd-catalysed asymmetric allylic transforma- phosphines, optically active phosphites and amido-
tions is rather limited. Meanwhile, catalytic asymmet- phosphites seem to be more versatile ligands.[1,2,8] In
ric allylic substitution serves as one of the most pow- general, the main advantages of phosphites include
erful methods for the regio- and stereoselective for- high p-acidity of the phosphorus atom, high resistance
À
À
À
À
mation of C C, C N, C O and C S bonds. The high to oxidative destruction, synthetic availability and
synthetic utility of this catalytic process is now well their low cost. For example, BINOL-based mono-
established through numerous efficient syntheses of phosphites, which are very efficient in asymmetric hy-
enantiopure natural and unnatural products.[19,20] drogenation, are only 2% of the price of the well-
Compounds La–Le (Figure 1) represent leading P known diphosphine BINAP.[28] Moreover, electronic
monodentate phosphite-type ligands for Pd-catalysed properties of the – traditional for phosphines – PPh2-
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Konstantin N. Gavrilov et al.
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Figure 2. Structure of the phosphine ligand MOP.
vide broad opportunities for fine tuning of their
donor-acceptor and steric properties by incorporation
of oxygen and nitrogen into the first coordination
sphere of phosphorus and wide variation of the O-
and N-containing building blocks.[1] This approach is
now considered most practical in developing one uni-
versal ligand for different types of asymmetric catalyt-
ic reactions. As an original framework for the new li-
gands, we chose phosphite and diamidophosphite de-
rivatives of rigid, axially chiral, monomethylated
BINOL.
Results and Discussion
Synthesis of P Monodentate Phosphite-Type Ligands
and their Palladium and Rhodium Complexes
Figure 1. P Monodentate phosphite-type ligands for Pd-cata-
lysed asymmetric allylation.
The novel MOP-type phosphites and diamidophos-
phites were easily obtained by direct phosphorylation
fragment can be regulated basically only by introduc- of (Sa)- or (Ra)-1-(2-methoxynaphthalen-1-yl)naphtha-
tion of electron-donor or electron-acceptor substitu- len-2-ol (O-methyl-BINOL) in the presence of Et3N
ents into the phenyl rings. In contrast, phosphites pro- in C6H6 (Scheme 1).
Scheme 1. Synthesis of phosphite-type ligands (Sa,Sa)-1, (Ra,Sa)-1 and (R,S,Sa)-2, (R,S,Ra)-2.
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MOP-Type Binaphthyl Phosphite and Diamidophosphite Ligands
FULL PAPERS
All compounds are white solids, which are stable sphere of the palladium atom.[36] It is interesting that
on prolonged storage. Since appropriate phosphory- the 31P NMR spectra of rhodium complexes 5a,b con-
lating reagents are readily available, new ligands can tain two doublets with close chemical shifts and JP,Rh
be prepared on a gram scale. It is worthy of note that coupling constants (see Experimental Section).
structures (R,S,Sa)-2 and (R,S,Ra)-2 combine together
two famous chiral auxiliaries: (S)-2-(anilinomethyl)-
pyrrolidine and BINOL.
Palladium-Catalysed Asymmetric Allylic Substitution
Although the crude P*-chiral ligands contain minor
epimers with an (S) configuration of the P*-stereo- Next we turned our attention to the applications of
centre [diastereoselectivity 94:6, d=128.9 and 119.6 (Sa,Sa)-1, (Ra,Sa)-1 and (R,S,Sa)-2, (R,S,Ra)-2 in the
for (R,S,Sa)-2; 97:3, d=125.7 and 118.4 for (R,S,Ra)- palladium complex-catalysed allylation (Scheme 3).
2], simple reprecipitation from CHCl3/hexane yields
stereoindividual (R,S,Sa)-2 and (R,S,Ra)-2. Therefore,
purified (R,S,Sa)-2 and (R,S,Ra)-2 represent single epi-
mers with a pseudo-equatorial orientation of the exo-
cyclic substituents at the phosphorus atom. The P*-
stereocentre has an (R) absolute configuration, which
2
is proved by the characteristic JC-8,P (33.5 and
35.7 Hz) coupling in the 13C NMR spectra of (R,S,Sa)-
2 and (R,S,Ra)-2 (see Experimental Section). The
2
magnitude of JC-8,P seems to be strongly controlled by
the dihedral angle associated with the lone-pair orbi-
tal of the phosphorus atom and C-8.[21,29–32] The
pseudo-equatorial location of exocyclic functions was
previously established for ligands La.[21]
To estimate the steric demands of the new com-
pounds, we calculated their Tolmanꢁs angles[33] by the
previously reported method using semi-empirical
quantum mechanical AM1 techniques with full opti-
misation of geometrical parameters.[34] The obtained
results show that (Sa,Sa)-1 and (Ra,Sa)-1 are character-
ised by moderate steric demands (q=1418), while
(R,S,Sa)-2 and (R,S,Ra)-2 are very bulky ligands (q=
Scheme 3. Enantioselective palladium-catalysed allylic sub-
stitution of (E)-1,3-diphenylallyl acetate 6.
1938). For comparison, Tolmanꢁs angle for P
(C6F5)3 is
1848, for P
A
In allylic sulfonylation of (E)-1,3-diphenylallyl ace-
Complexation of the novel phosphites and diamido- tate 6 with p-TolSO2Na as the S-nucleophile diamido-
phosphites with [Pd(allyl)Cl]2 (in the presence of phosphite (R,S,Ra)-2 showed excellent activity and
AgBF4) and [Rh(COD)2]BF4 produced cationic enantioselectivity (Table 1, entries 4–6). It should be
Pd(II) complexes (Scheme 2). noted that chiral allylic sulfones are exceptionally ver-
AHCTREUNG
AHCTREUNG
These compounds are stable in air and well soluble satile intermediates in organic synthesis[20] and that
in common organic media. According to the 31P NMR the 99% enantioselectivity achieved with (R,S,Ra)-2
data (see Experimental Section), 3a,b and 4a,b dem- (Table 1, entry 4) is superior to the highest previously
onstrate fast interconversion of the exo and endo iso- known result (97% ee) for allylic sulfonylation ob-
mers or the absence of one of them.[21] AB spin sys- tained with other P*-chiral diamidophosphites.[21]
tems in the spectra of 3a,b indicate non-equivalence (R,S,Sa)-2 afforded product 7 in opposite absolute
of two P monodentate ligands in the coordination configuration but with lower enantioselectivity
Scheme 2. Synthesis of complexes 3a,b, 4a,b and 5a,b.
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Table 1. Palladium-catalysed allylic sulfonylation of 7 with p-TolSO2Na (208C, 48 h) and allylic alkylation of 6 with dimethyl
malonate (BSA, KOAc, 208C, 48 h).
Entry
Catalyst
L/Pd
Solvent
Conv. [%][a]
ee [%]
allylicsulfonylation
1
2
3
4
5
6
[Pd
[Pd
4a
[Pd
[Pd
U
A
1/1
2/1
2/1
1/1
2/1
2/1
THF
THF
THF
THF
THF
THF
71
63
90
95
91
95
65 (S)
73 (S)
86 (S)
99 (R)
95 (R)
92 (R)
A
G
4b
allylicalkylation
7
8
9
[Pd
[Pd
3a
[Pd
[Pd
3b
U
A
1/1
2/1
2/1
1/1
2/1
2/1
2/1
1/1
1/1
2/1
2/1
2/1
2/1
1/1
1/1
2/1
2/1
2/1
2/1
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
THF
THF
CH2Cl2
THF
CH2Cl2
THF
CH2Cl2
THF
CH2Cl2
THF
53
32
71
40
60
59
38
75
49
77
54
79
97
71
76
66
76
77
99
67 (S)
61 (S)
56 (S)
52 (S)
30 (S)
56 (S)
72 (S)
94 (R)
15 (R)
95 (R)
13 (R)
94 (S)
91 (S)
99 (R)
85 (S)
95 (R)
91 (S)
84 (S)
98 (S)
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
3b
[Pd
[Pd
[Pd
[Pd
4a
4a
[Pd
[Pd
[Pd
[Pd
4b
G
G
CH2Cl2
THF
CH2Cl2
4b
[a]
Isolated yield of 7 in allylic sulfonylation.
(Table 1, entries 1–3), probably because of the mis- chiral P monodentate phosphite-type ligands, as it ex-
matched combination of the (2R,5S)-phosphocentre ceeds the previously reported enantiomeric excess (up
with (Sax)-O-methyl-BINOL fragment. Rather unex- to 97%) shown by the compounds La–Ld.
pectedly, phosphites (Sa,Sa)-1 and (Ra,Sa)-1 {with [Pd-
(allyl)Cl]2, L/Pd=1 or 2} and their palladium com- {with [Pd
plexes 3a,b gave no conversion in the synthesis of 7. complexes 3a,b were tested in Pd-catalysed allylic
Monodentate phosphites (Sa,Sa)-1 and (Ra,Sa)-1
A
ACHTREUNG
On the contrary, in the allylic alkylation of 6 with amination of 6 with pyrrolidine as the N-nucleophile
dimethyl malonate as the C-nucleophile (Sa,Sa)-1 and (in THF and CH2Cl2), the ees generally being moder-
(Ra,Sa)-1 showed good conversion (up to 71%) and ee ate to poor: up to 57% (S) and 39% (R), respectively.
(up to 72%, Table 1, entries 7–13). Since (S)-8 was The configuration of the BINOL-based phosphocycle
isolated in all trials, one can conclude that absolute determines the absolute configuration of product 9.
configuration of the product is determined by the pe- P*-Chiral diamidophosphites (R,S,Sa)-2 and (R,S,Ra)-
ripheral (Sa)-O-methyl-BINOL group. (R,S,Sa)-2 and 2 gave better ees of up to 83 and 97% (Table 2, en-
(R,S,Ra)-2 were found to be highly efficient stereose- tries 4 and 9). The (2R,5S)-phosphocentre/(Ra)-O-
lectors, as up to 95 and 99% ee, respectively, were ob- methyl-BINOL represents the matched case. Here
tained (Table 1, entries 16 and 20). The enantiomeric again the stereochemistry of the phosphocentre dic-
excess depends significantly on the solvent used: prac- tates the stereochemistry of product 9. Although the
tically in all cases THF is the optimal solvent. On the ratio of ligand to Pd does not have a profound influ-
contrary, the L/Pd molar ratio has basically no effect ence on the enantioselectivity, the highest results
on enantioselectivity. The absolute configuration of were obtained at L/Pd=2. In general, CH2Cl2 proved
product 8 depends not only on the applied ligand, but to be the solvent of choice for (R,S,Sa)-2, while for
also on the solvent used and counterion in the catalyt- (R,S,Ra)-2 THF gave better results.
ic complex (Table 1, entries 16 and 18, 20 and 21, 22
In a closely related Pd-catalysed allylic amination
and 24). The excellent enantioselectivity (99%) ach- of 6 with dipropylamine (Sa,Sa)-1 and (Ra,Sa)-1 dem-
ieved in this reaction is the best result for all known onstrated somewhat higher enantioselectivity of up to
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MOP-Type Binaphthyl Phosphite and Diamidophosphite Ligands
FULL PAPERS
Table 2. Palladium-catalysed allylic amination of 6 with pyrrolidine and di-n-propylamine (208C, 48 h).
Entry
Catalyst
L/Pd
Solvent
Conv. [%]
ee [%]
with pyrrolidine
1
2
3
4
5
6
7
8
[Pd
[Pd
[Pd
[Pd
4a
4a
[Pd
[Pd
[Pd
C
N
1/1
1/1
2/1
2/1
2/1
2/1
1/1
1/1
2/1
2/1
2/1
2/1
THF
CH2Cl2
THF
CH2Cl2
THF
CH2Cl2
THF
CH2Cl2
THF
CH2Cl2
THF
CH2Cl2
95
100
97
100
48
97
81
42
100
100
94
57 (R)
60 (R)
35 (R)
83 (R)
71 (R)
65 (R)
94 (R)
88 (R)
97 (R)
86 (R)
83 (R)
45 (R)
9
U
N
10
11
12
[Pd
4b
4b
95
with dipropylamine
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
[Pd
[Pd
3a
[Pd
[Pd
3b
[Pd
[Pd
[Pd
[Pd
4a
C
N
1/1
2/1
2/1
1/1
2/1
2/1
1/1
1/1
2/1
2/1
2/1
2/1
1/1
1/1
2/1
2/1
2/1
2/1
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
THF
CH2Cl2
THF
CH2Cl2
THF
CH2Cl2
THF
CH2Cl2
THF
CH2Cl2
THF
CH2Cl2
26
21
100
40
39
100
95
100
65
100
64
77
4 (À)
2 (À)
44 (À)
50 (+)
74 (+)
6 (+)
95 (+)
95 (+)
93 (+)
94 (+)
74 (+)
30 (+)
37 (+)
23 (+)
51 (+)
50 (+)
92 (+)
66 (+)
A
G
4a
[Pd
[Pd
[Pd
[Pd
4b
65
100
100
92
68
90
4b
74% ee (Table 2, entries 13–18). (Ra)-BINOL/(Sa)-O- entries 20 and 29) at quantitative conversion in the
methyl-BINOL is the matched case (74% ee) in con- case of (R,S,Sa)-2. This is the best result ever achieved
trast to the mismatched combination (Sa)-BINOL/ in the discussed reaction.[37] The molar ratio L/Pd=1
(Sa)-O-methyl-BINOL (44% ee, Table 2, entries 15 and CH2Cl2 as reaction medium are crucial for high
and 17). Both ligands (R,S,Sa)-2 and (R,S,Ra)-2 gave asymmetric induction in the case of diamidophosphite
10 with close optical purity 95 and 92% ee (Table 3, (R,S,Sa)-2, while for (R,S,Ra)-2 optimal conditions in-
Table 3. Palladium-catalysed deracemisation of 11 (CH2Cl2, NaHCO3, (Bu)4NHSO4, 208C, 48 h).
Entry
Catalyst
L/Pd
Conv. [%]
ee [%]
1
2
3
4
5
6
7
8
9
[Pd
[Pd
[Pd
C
U
1/1
2/1
2/1
1/1
2/1
1/1
2/1
1/1
2/1
1/1
30
97
68
72
67
74
98
77
97
70
20 (R)
94 (R)
81 (R)
79 (R)
73 (R)
14 (R)
95 (R)
46 (R)
96 (R)
30 (R)
A
U
ACHTREUNG
C
G
ACHTREUNG
N
U
ACHTREUNG
4a
[Pd
[Pd
G
ACHTREUNG
10
A
G
ACHTREUNG
[a]
With substrate 6.
In THF.
[b]
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Konstantin N. Gavrilov et al.
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clude L/Pd=2 and THF as solvent. Analogously to 9, as the palladium precursor gave better results (see en-
the stereochemistry of 10 is determined by the tries 2, 5, 8 and 10 in Table 3), the molar ratio L/Pd=
(2R,5S)-phosphocentre of ligands (R,S,Sa)-2 and 2 being optimal in the case of p-allyl palladium com-
(R,S,Ra)-2.
plexes. When allyl acetate 6 was used as a substrate
instead of allyl carbonate 11, the conversion and ee
decreased significantly (Table 3, entries 2 and 3). It is
necessary to note that known methods of synthesis
can provide an important chiral alcohol chalcol 12
Palladium-Catalysed Deracemisation
The complete conversion of a racemate to one enan- only in 75–92% ee.[39–45] Accordingly, Pd-catalysed de-
tiomer without intermediate separation of materials racemisation of ethyl (E)-1,3-diphenylallyl carbonate
(deracemisation) is one of the current challenges in 11 with participation of inexpensive diamidophos-
asymmetric synthesis. Allylic alcohols are targets of phites (R,S,Sa)-2 and (R,S,Ra)-2 is a highly efficient
high synthetic importance because of their many ap- method of preparation of 12 with a record high enan-
plications (see[38] and the references cited therein). tioselectivity.
Their deracemisation can be achieved by Pd-catalysed
substitution of allylic esters with carboxylate ions in
the presence of a chiral ligand for the palladium Rhodium-Catalysed Asymmetric Hydrogenation
atom. The deracemisation of allylic esters is usually
carried out in CH2Cl2/H2O (9:1),[38] but we chose The efficacy of the MOP-type phosphite and diamido-
water-free conditions with formation of the phosphite ligands was also evaluated in the Rh-cata-
(Bu)4NHCO3 salt in situ directly in organic media lysed asymmetric hydrogenation of dimethyl itaconate
(Scheme 4).
13 (Scheme 5). Some results are summarised in
Table 4.
Scheme 5. Enantioselective rhodium-catalysed hydrogena-
tion of dimethyl itaconate 13.
Scheme 4. Enantioselective palladium-catalysed deracemisa-
tion of ethyl (E)-1,3-diphenylallyl carbonate 11.
This approach excludes an ester hydrolysis step
Ligands (R,S,Sa)-2 and (R,S,Ra)-2 exhibited moder-
from the catalytic cycle[38] and makes it possible to ate to good enantioselectivity and low to moderate
apply the hydrogen carbonate ion as an external nu- conversion. Using P-chirogenic ligand (R,S,Ra)-2 gave
cleophile. What is even more important, use of water- 90% ee (Table 4, entry 3), while the asymmetric in-
sensitive organophosphorus ligands becomes possible. duction and activity of its diastereoisomer (R,S,Sa)-2
P*-Chiral
diamidophosphites
(R,S,Sa)-2
and was rather low. Focusing on ligand (R,S,Ra)-2, the
(R,S,Ra)-2 resulted in 95–96% ee and 97–98% conver- enantioselectivities were increased when the reactions
sion (Table 3), which stands in contrast to the medio- were carried out in CH2Cl2 (90% ee) instead of ethyl
cre results obtained with phosphites (Sa,Sa)-1 and acetate (62% ee) (Table 4, entries 3 and 4). Unfortu-
(Ra,Sa)-1 (not more than 47% ee and 50% of conver- nately, phosphite (Sa,Sa)-1 did not show any activity
sion). Table 3 shows some remarkable trends. Both li- under the same conditions, but (Ra,Sa)-1 exhibited
gands (R,S,Sa)-2 and (R,S,Ra)-2 provided practically very low conversion and enantioselectivity (in CH2Cl2
equally high levels of asymmetric induction and the 18% and 8%, respectively). The results achieved with
(R)-configuration of 12 (Table 3, entries 2, 7 and 9). P*-chiral diamidophosphite (R,S,Ra)-2 are rather re-
The use of [Pd
N
N
Table 4. Rhodium-catalysed hydrogenation of 13 (5 bar H2, 208C, 20 h, [Rh(COD)2]BF4 as precatalyst).
A
Entry
Ligand
Solvent
Conv. [%]
ee [%]
1
2
3
4
C
CH2Cl2
EtOAc
CH2Cl2
EtOAc
0
-
27
63
53
38 (S)
90 (S)
62 (S)
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MOP-Type Binaphthyl Phosphite and Diamidophosphite Ligands
FULL PAPERS
Enantiomeric excesses of product 7 were determined
using HPLC [(R,R)-WHELK-01 column] according to the
literature.[50] Conversion of substrate 6[51] and optical purity
of products 8[51], 9[52] and 10[53] were determined using
HPLC (Daicel Chiralcel OD-H column) as described previ-
ously. Conversion of substrate 11 and ee of product 12 were
determined using HPLC (Daicel Chiralcel OD-H column)
according to the literature.[41] The ee values of product 14
were determined using HPLC (Daicel Chiralcel OD-H
column) according to the literature.[54]
All reactions were carried out under a dry argon atmos-
phere in freshly dried and distilled solvents; Et3N, pyrroli-
dine and dipropylamine were twice distilled over KOH and
then over a small amount of LiAlH4 before use. 1-(2-Me-
thoxynaphthalen-1-yl)naphthalen-2-ol was synthesised using
literature procedures.[55] Phosphorylating reagents (Sa or
metric hydrogenation when P monodentate phos-
phite-type ligands without BINOL and biphenol moi-
eties showed satisfactory enantioselectivity.[46–49]
Conclusions
In summary, stereoindividual MOP-type binaphthyl
monodentate phosphite and diamidophosphite ligands
have been prepared for the first time by applying the
cheap and readily accessible O-methyl-BINOL as
common precursor. Bulky P*-chiral diamidophos-
phites based on inexpensive (S)-2-(anilinomethyl)pyr-
rolidine can successfully be applied in the Pd-cata-
lysed allylic substitution reactions of (E)-1,3-dipheny-
lallyl acetate with S-, C- and N-nucleophiles and in
the Rh-catalysed hydrogenation of dimethyl itaco-
nate. On the whole, epimer (R,S,Ra)-2 provides higher
enantioselectivity in both processes thanks to the
matched combination of the (2R,5S)-phosphocentre
with the (Ra)-O-methyl-BINOL fragment. In the Pd-
catalysed deracemisation of ethyl (E)-1,3-diphenylall-
yl carbonate, both (R,S,Ra)-2 and (R,S,Sa)-2 show high
asymmetric induction. In general, record high optical
yields were obtained in all three tested asymmetric re-
actions: allylic substitution of (E)-1,3-diphenylallyl
acetate with sodium p-toluenesulfinate (99% ee) and
with dipropylamine (95% ee), and in the deracemisa-
tion of ethyl (E)-1,3-diphenylallyl carbonate (96%
ee). BINOL-based phosphites (Sa,Sa)-1 and (Ra,Sa)-1
demonstrated moderate enantioselectivity only in the
Pd-catalysed allylation of (E)-1,3-diphenylallyl acetate
with dimethyl malonate (72% ee) and dipropylamine
(74% ee). Presumably, other types of asymmetric
transformations might be more suitable for these li-
gands. Thus, Pd-catalysed hydrosilylation-oxidation
Ra)-2-chlorodinaphtho[2,1-d:1’,2’-f]
and (2R,5S)-2-chloro-3-phenyl-1,3-diaza-2-phosphabicyclo-
[3.3.0]octane were prepared as published.[21,56] [Rh-
[59]
A
AHCTREUNG
[57]
[58]
(COD)2]BF4
,
[Pd
U
and [Pd2(dba)3]·CHCl3
N
were prepared as described earlier. Cationic palladium com-
plexes 3a,b and 4a,b were synthesised analogously to the
known procedures.[21] Catalytic experiments: allylic sulfony-
lation of substrate 6 with sodium p-toluenesulfinate, allylic
alkylation with dimethyl malonate, allylic amination with
pyrrolidine, and allylic amination with dipropylamine were
performed according to the appropriate procedures.[21,36,37]
Starting substrates 6 and 11 were synthesised as pub-
lished.[58,60] Dimethyl itaconate, dimethyl malonate, BSA
[N,O-bis(trimethylsilyl)acetamide] and sodium p-toluenesul-
finate were purchased from Aldrich and Acros Organics
and used without further purification.
General Procedure for the Synthesis of Ligands
(Sa,Sa)-1, (Ra,Sa)-1, (R,S,Sa)-2 and (R,S,Ra)-2
Asolution of Et 3N (1.9 mmol) and 1-(2-methoxynaphtha-
len-1-yl)naphthalen-2-ol (1.8 mmol) in benzene (10 mL) was
added to a vigorously stirred solution of the appropriate
and Rh-catalysed addition of arylboronic acids are phosphorylating reagent (1.8 mmol) in benzene (20 mL).The
mixture was heated with stirring to boiling and then cooled
down to 208C. Solid Et3N·HCl was filtered off; benzene was
removed under reduced pressure (40 Torr). The residue was
dissolved in 1 mL of CHCl3 and precipitated with hexane
(12 mL), filtered and dried under vacuum (1 Torr) for 2 h.
(S)-2-{(S)-[1-(2-Methoxynaphthalen-1-yl)]naphthalen-2-
currently under investigation in our laboratory, as is
the expansion of our MOP-type chiral phosphite
ligand library.
oxy}dinaphtho[2,1-d:1’,2’-f][1,3,2]dioxaphosphepine [(Sa,Sa)-
A
1]: White solid; yield: 1.042 g (94%); mp 151–1538C; [a]2D0:
+72.6 (c 1, CHCl3); 1H NMR (CDCl3): d=3.72 (3H, s),
7.14–7.55 (17H, m), 7.68–8.09 (7H, m); 13C NMR (CDCl3):
Experimental Section
General Remarks
2
2
d=155.3, 147.6 (d, JC,P =7.3 Hz), 147.5 (d, JC,P =4.4 Hz),
146.9, 134.2, 132.6, 132.2, 131.3, 130.9, 130.8, 130.0, 129.9,
129.4, 129.2, 128.9, 128.2, 128.1, 127.9, 127.8, 126.8, 126.6,
126.5, 126.1, 125.9, 125.8, 125.1, 124.9, 124.8, 124.7, 124.6,
123.9, 123.6, 122.4, 121.7, 121.5, 120.9, 120.8, 117.9, 56.2
(OCH3); 31P NMR (CDCl3): d=144.7; MS (EI): m/z (%)=
614 (18, [M ]+), 583 (100, [MÀMeO]+), 268 (81,
31P and 13C spectra were recorded on a Bruker AMX-400 in-
strument (162.0 MHz for 31P and 100.6 MHz for 13C). The
complete assignment of all the resonances in 13C NMR spec-
tra was achieved using DEPT techniques. Chemical shifts
(ppm) are given relative to Me4Si (13C NMR) and 85%
H3PO4 in D2O (31P NMR). Mass spectra were recorded with
a Varian MAT 311 spectrometer (EI) and a Finnigan LCQ [C20H12O]+); anal. calcd. for C41H27O4P: C 80.12, H 4.43, P
Advantage spectrometer (electrospray ionisation technique,
ESI). Elemental analyses were performed at the Laboratory
of Microanalysis (Institute of Organoelement Compounds,
Moscow).
5.04; found: C 80.33, H 4.68, P 4.92.
(R)-2-{(S)-[1-(2-Methoxynaphthalen-1-yl)]naphthalen-2-
oxy}dinaphtho[2,1-d:1’,2’-f]
A
[(Ra,Sa)-1]: White solid; yield: 1.064 g (96%); mp 196–
Adv. Synth. Catal. 2007, 349, 1085 – 1094
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Konstantin N. Gavrilov et al.
FULL PAPERS
1988C; [a]20: À84.55 (c 1, CHCl3); 1H NMR (CDCl3): d=
{Pd
C
N
3.79 (3H, Ds), 7.13–7.53 (17H, m), 7.72–8.15 (7H, m);
2
13C NMR (CDCl3): d=155.3, 147.7 (d, JC,P =8.8 Hz), 147.2
(d, 2JC,P =4.4 Hz), 147.0, 134.1, 133.8, 132.5, 132.0, 131.3,
131.0, 130.9, 130.1, 130.0, 129.5, 129.1, 128.5, 128.1, 128.0,
127.8, 126.7, 126.6, 126.5, 126.2, 126.0, 125.9, 125.7, 125.4,
124.9, 124.8, 124.5, 124.2, 124.1, 124.0, 123.9, 123.6, 122.4,
121.6, 121.5, 117.8, 55.9 (OCH3); 31P NMR (CDCl3): d=
146.1; MS (EI): m/z (%)=614 (25, [M ]+), 583 (100,
[MÀMeO]+), 268 (90, [C20H12O]+); anal. calcd. for
C41H27O4P: C 80.12, H 4.43, P 5.04; found: C 80.24, H 4.33,
P 5.29.
{Pd
mp 180–1828C (dec.); 31P NMR (CDCl3): d=115.1; MS
(ESI): m/z (%)=1156 (100, [MÀBF4]+); anal. calcd. for
C67H63BF4N4O4P2Pd: C 64.72, H 5.11, N 4.51; found: C
64.83, H 5.22, N 4.41.
General Procedure for the Synthesis of Rhodium
Complexes
ACHTREUNG
AHCTREUNG
Asolution of the relevant ligand ( R,S,Sa)-2 or (R,S,Ra)-2
(0.101 g, 0.2 mmol) in CH2Cl2 (10 mL) was added dropwise
during 40 min to a vigorously stirred solution of [Rh-
[(R,S,Sa)-2]: White solid; yield: 0.735 g (81%); mp 156–
1
1588C; [a]2D0: +129.8 (c 1, CHCl3); H NMR (CDCl3): d=
1.49 (1H, m), 1.74 (2H, m), 2.08 (1H, m), 2.94–3.28 (2H,
m), 3.35–3.62 (3H, m), 3.73 (3H, s), 6.79 (1H, t, J=7.2 Hz),
7.07–7.93 (16H, m); 13C NMR (CDCl3): d=155.1, 149.6,
144.8 (d, 2JC,P =16.1 Hz), 134.0, 133.9, 130.2, 129.3, 128.7,
128.6, 128.5, 127.7, 127.5, 126.1, 125.7, 125.6, 125.5, 124.2,
A
mixture was stirred for additional 1 h and concentrated at
reduced pressure to a volume of ca. 0.5 mL and ether
(15 mL) was added. The precipitated solid was separated by
centrifugation, washed with ether (2”10 mL) and dried
under vacuum (1 Torr) for 1 h.
3
124.0, 123.1, 123.0, 122.9, 119.4, 118.6, 114.7 (d, JC2,P =13.1),
2
62.0 (d, JC,P =8.0 Hz, C-5), 56.4 (OCH3), 53.3 (d, JC,P =6.6
2
{Rh
N
N
Hz, C-4), 47.2 (d, JC,P =33.5 Hz, C-8), 30.9 (C-6), 25.8 (d,
0.251 g (96%); mp 143–1478C (dec.); 31P NMR (CDCl3):
3JC,P =3.7 Hz, C-7); 31P NMR (CDCl3): d=128.9; MS (EI):
m/z (%)=504 (8, [M]+), 473 (39, [MÀMeO]+), 300 (14,
1
d=106.1 (d, 1JP, Rh =229.7 Hz, 21%), 99.9 (d, JP,Rh
=
[C21H16O2]+),
[268
(11,
[C20H12O]+),
205
(100,
213.0 Hz, 79%); MS (ESI): m/z (%)=1112 (100,
[MÀBF4ÀCOD]+), 1194 (96, [Rh
C
[MÀC21H15O2]+); anal. calcd. for C32H29N2O2P: C 76.17, H
5.79, N 5.55; found: C 76.42, H 6.0, N 5.49.
ACHTREUNG
{Rh
C
G
AHCTREUNG
[(R,S,Ra)-2]: White solid; yield: 0.762 g (84%); mp 130–
d=106.4 (d, 1JP, Rh =228.3 Hz, 70%), 100.7 (d, JP,Rh
=
1
1348C; [a]2D0: À198.25 (c 1, CHCl3); H NMR (CDCl3): d=
1
214.1 Hz, 30%); MS (ESI): m/z (%)=1112 (100,
1.53 (1H, m), 1.82 (2H, m), 1.98 (1H, m), 3.09–3.32 (2H,
m), 3.41–3.68 (3H, m), 3.72 (3H, s), 6.81 (1H, t, J=7.3 Hz),
7.18–7.90 (16H, m); 13C NMR (CDCl3): d=155.2, 149.8 (d,
[MÀBF4ÀCOD]+), 1194 (82, [Rh
(CH3CN)2(L)2]+); anal.
calcd. for C72H70BF4N4O4P2Rh: C 66.16, H 5.40; found: C
66.41, H 5.49.
2JC,P =6.6 Hz), 145.0 (d, JC,P =16.8 Hz), 133.9, 133.8, 130.2,
2
129.2, 128.8, 128.7, 128.5, 127.7, 127.5, 125.9, 125.8, 125.7,
125.6, 124.1, 123.9, 123.1, 122.9, 122.8, 119.3, 118.6, 114.7 (d,
3JC,P =12.4 Hz), 62.2 (d, 2JC,P =9.5 Hz, C-5), 56.6 (OCH3),
53.6 (d, JC,P =7.3 Hz, C-4), 47.0 (d, JC,P =35.7 Hz, C-8), 31.4
(C-6), 25.7 (d, 3JC,P =4.4 Hz, C-7); 31P NMR (CDCl3): d=
125.7; MS (EI): m/z (%)=504 (6, [M]+), 473 (50,
[MÀMeO]+), 300 (9, [C21H16O2]+), [268 (15, [C20H12O]+),
205 (100, [MÀC21H15O2]+); anal. calcd. for C32H29N2O2P: C
76.17, H 5.79, N 5.55; found: C 76.31, H 5.88, N 5.81.
General Procedure for the Hydrogenation of
Dimethyl Itaconate
2
2
[Rh(COD)2]BF4 (2.4 mg; 0.006 mmol), the appropriate
A
ligand (0.012 mmol), dimethyl itaconate (0.1 g, 0.6 mmol)
and the appropriate solvent (3 mL) were placed in a 25-mL
autoclave under an atmosphere of argon. The autoclave was
closed and flushed three times with hydrogen, and then the
hydrogenation was performed at room temperature under
an H2 pressure of 5 bar during 20 h. The reaction mixture
was diluted with hexane (5 mL), passed through a short
silica gel plug using hexane as the eluent and analysed by
HPLC and 1H NMR.
Palladium Complexes
{Pd
N
N
160–1628C (dec.); 31P NMR (CDCl3): d=138.6 and 137.2
General Procedure for the Deracemisation of Ethyl
(E)-1,3-Diphenylallyl Carbonate
2
(AB system, each d, JP,Pꢁ =111.5 Hz); MS (ESI): m/z (%)=
1377 (16, [MÀBF4]+), 706 (100, [Pd(L)ÀMe]+); anal. calcd.
for C85H59BF4O8P2Pd: C 69.76, H 4.06, P 4.23; found: C
70.09, H 4.2, P 4.03.
Asolution of [Pd
A
AHCTREUNG
{Pd
C
G
ligand (0.02 mmol, 0.04 mmol) in 5 mL of the appropriate
solvent was stirred for 40 min [alternatively, the presynthes-
ised complex 4a (0.02 mmol) was dissolved in appropriate
solvent (5 mL)]. Then ethyl (E)-1,3-diphenylallyl carbonate
(0.141 g, 0.5 mmol) was added and the solution stirred for
15 min, then NaHCO3 (0.73 g, 8.7 mmol) and (Bu)4NHSO4
140.0 (AB system, each d , JP,Pꢁ =108.2 Hz); MS (ESI): m/z
(%)=1377 (23, [MÀBF4]+), 706 (100, [Pd(L)ÀMe]+); anal.
calcd. for C85H59BF4O8P2Pd: C 69.76, H 4.06, P 4.23; found:
C 69.92, H 3.97, P 4.08.
1092
asc.wiley-vch.de
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Adv. Synth. Catal. 2007, 349, 1085 – 1094

MOP-Type Binaphthyl Phosphite and Diamidophosphite Ligands
FULL PAPERS
(0.289 g, 0.85 mmol) were added. The reaction mixture was
stirred for 48 h. After that, the resulting solution was passed
through a short Celite plug using CH2Cl2 (10 mL) as the
eluent and analysed by HPLC.
[21] V. N. Tsarev, S. E. Lyubimov, A. A. Shiryaev, S. V. Zhe-
glov, O. G. Bondarev, V. A. Davankov, A. A. Kabro,
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Org. Chem. 2004, 2214–2222.
[22] M. D. K. Boele, P. C. J. Kamer, M. Lutz, A. L. Spek,
J. G. de Vries, P. W. N. M. van Leeuwen, G. P. F. van
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[23] K. N. Gavrilov, S. E. Lyubimov, P. V. Petrovskii, S. V.
Zheglov, A. S. Safronov, R. S. Skazov, V. A. Davankov,
Tetrahedron 2005, 61, 10514–10520.
Acknowledgements
The authors thank Dr. A.V. Korostylev (ASINEX Ltd.,
Moscow) for his assistance in the preparation of the manu-
script. The authors are sincerely grateful to Prof. H.-J. Gais
(Institut fur Organische Chemie der RWTH Aachen, Germa-
ny) for fruitful discussion on the technique of Pd-catalysed
deracemisation. This work was supported by the INTAS
Open Call 05–1000008–8064 Grant and RFBR Grant No.
04–03–39017.
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