P-chiral monodentate diamidophosphites - New and efficient ligands for palladium-catalysed asymmetric allylic substitution

Article abstract of DOI:10.1002/ejoc.200300694

Novel P*-monodentate diamidophosphite ligands have been prepared by a one-step phosphorylation of alcohols or amines. Both the electronic and the steric demands of the ligands have been estimated quantitatively. Neutral [Pd(allyl)Cl(L)] and cationic [Pd(a

Full text of DOI:10.1002/ejoc.200300694

FULL PAPER
P-Chiral Monodentate Diamidophosphites ؊ New and Efficient Ligands for
Palladium-Catalysed Asymmetric Allylic Substitution
Vasily N. Tsarev,*[a] Sergey E. Lyubimov,[b] Alexei A. Shiryaev,[b] Sergey V. Zheglov,[b]
Oleg G. Bondarev,[a] Vadim A. Davankov,[a] Anzhelika A. Kabro,[a] Sergey K. Moiseev,[a]
Valery N. Kalinin,[a] and Konstantin N. Gavrilov[b]
Keywords: Allylic substitution / Asymmetric catalysis / P ligands / Palladium / Rhodium
Novel P*-monodentate diamidophosphite ligands have been
prepared by a one-step phosphorylation of alcohols or
amines. Both the electronic and the steric demands of the
acetate with NaSO2pTol (up to 97% ee), PhCH2NH2 (up to
95% ee) and CH2(CO2Me)2 (up to 97% ee). Application of
the P*-monodentate diamidophosphites to the asymmetric
catalytic synthesis of chiral carborane derivatives has also
ligands have been estimated quantitatively. Neutral [Pd(al-
−
lyl)Cl(L)] and cationic [Pd(allyl)(L)2]+ BF4 complexes have been demonstrated.
been obtained by starting from [Pd(allyl)Cl]2. The new li-
gands have demonstrated high enantioselectivity in the Pd- ( Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
catalysed allylic substitution reactions of 1,3-diphenylallyl
Germany, 2004)
Introduction
The last five years have been characterized by significant
progress in the use of chiral phosphites in asymmetric metal
complex catalysis.[1Ϫ3] First and foremost this relates to
monodentate phosphites and phosphoramidites of the types
depicted in Figure 1.
Almost quantitative enantioselectivity has been achieved
in the Rh-catalysed hydrogenation of prochiral unsaturated
substrates in the presence of La[4Ϫ6,7] and Lb.[8,9] At present,
these BINOL-derived ligands compete successfully with the
P,P-bidentate phosphanes that previously dominated in this
field. Notably, La is 50 times cheaper than BINAP.[5]
Some more impressive results have been provided by
phosphoramidites Lb in the Cu-catalysed conjugate ad-
dition of organometallic reagents to enones[10] and in Ni-
catalysed hydrovinylation.[11] In the Pd-catalysed
hydrosilylationϪoxidation of vinyl arenes, Lb afforded the
highest enantioselectivity so far Ϫ up to 99% ee in the case
of styrene.[12]
Figure 1. Some well-known efficient P-monodentate chiral phos-
phites and phosphoramidites
easily available biphenols. Compound Lc provided a 99% ee
in the Cu-catalysed conjugate addition of R2Zn to cyclo-
hexenone,[13,14] and Ld yielded up to 75% ee in the Rh-cata-
lysed hydrogenation of dimethyl itaconate.[15]
TADDOL-derived phosphoramidites Le have been ap-
plied to good effect in Cu-catalysed conjugate addition[16]
and Pd-catalysed intramolecular Heck reactions.[17] High
ees were also achieved in the Rh-catalysed hydrogenation
of unsaturated carboxylic acids with the phosphacyclanes
Lf, derived from -mannitol and closely related to Le.[18]
Of particular interest is the contribution of monodentate
phosphites and phosphoramidites to the catalytic allylic
The design of Lc and Ld put into practice an attractive
idea to replace the BINOL chiral scaffold with cheap and
[a]
A. N. Nesmeyanov Institute of Organoelement Compounds,
Russian Academy of Sciences,
28 Vavilova str., Moscow, 119991, Russia
Fax: (internat.) ϩ 7-095-135-6471
E-mail: tsarev@ineos.ac.ru
[b]
Department of Chemistry, Ryazan State Pedagogic University,
46 Svoboda str., Ryazan, 390000, Russia
Fax: (internat.) ϩ 7-0912-775-498
E-mail: chem@ttc.ryazan.ru
Supporting information for this article is available on the
WWW under http://www.eurjoc.org or from the author.
2214
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
DOI: 10.1002/ejoc.200300694
Eur. J. Org. Chem. 2004, 2214Ϫ2222

P-Chiral Monodentate Diamidophosphites
FULL PAPER
Table 1. 31P NMR chemical shifts (CDCl3) and cone angles θ (deg.)
of ligands 3aϪj
substitution processes. Ir-catalysed alkylations of a variety
of dissymmetrical substrates with dimethyl malonate were
reported to give up to 86% ee with Lb and 96% ee with
La.[19Ϫ21] Slightly better results (up to 97% ee) have been
obtained with phosphoramidites Lb by use of amines[22] or
phenoxides[23] as nucleophiles. To the best of our knowl-
edge, there have been no reports on efficient catalytic appli-
cations of monodentate phosphites or phosphoramidites
bearing a P*-stereogenic atom. Monodentate chiral phos-
phites and phosphoramidites have also never been em-
ployed in Pd-catalysed allylic substitution reactions, even
Ligand
δP
θ
(RP)-3a
123.1
123.9
133.3
128.4
114.5
127.1
114.9
126.7
112.3
129.5
121.7
123.5
114.4
117.3
114.8
95.2
122
134
152
156
(RP)-3b
(RP)-3c
(RP)-3d (82%)[a]
(SP)-3d (18%)
(RP)-3e (91%)
(SP)-3e (9%)
(RP)-3f (74%)
137
168
163
163
though palladium is usually the metal of choice in catalytic (SP)-3f (26%)
allylation.[24] Since ligands bearing chiral donor atoms are
(RP)-3g (93%)
(SP)-3g (7%)
reputed to be good stereoselectors,[25] we present here a
(RP)-3h (98%)
series of new P*-chiral ligands and the results of their appli-
(SP)-3h (2%)
cation in various Pd-catalysed allylic substitution reactions.
(RP)-3i
(RP)-3j (97%)
(SP)-3j (3%)
137
149
[a]
Percentage of P* epimers.
Results and Discussion
The 31P NMR spectroscopic data for 3aϪj are summa-
rized in Table 1. While ligands 3a؊c and 3i are formed as
single stereoisomers, 3d؊h and 3j each contain from 2 to
26% of the second stereoisomer. In all cases, the major ster-
eoisomer has a pseudoequatorial orientation of the ex-
ocyclic substituent at the phosphorus atom (i.e., the R con-
Monodentate diamidophosphites 3aϪj were synthesized
by a one-step phosphorylation of the corresponding al-
cohols or amines 2aϪj with (2R,5S)-1,3-diaza-2-chloro-3-
phenyl-2-phosphabicyclo[3.3.0]octane (1) (Scheme 1).
figuration at the P* stereocenter). This was concluded from
[26,27] 2
the characteristic
J
values (34.3Ϫ41.2 Hz) in the
C(8),P
13C NMR spectra of 3a؊j (see Table 2 and the Exp. Sect.).
There is a correlation between the JC(8),P values and the
2
dihedral angle between the lone pair (LP) of the phos-
phorus atom and C(8).[28] If the LP of the phosphorus atom
and C(8) are cis to each other (i.e., the substituent X has a
2
pseudoequatorial orientation, Scheme 1), the JC(8),P value
is maximum. In contrast, the minimum values of the 2JC(8),P
correspond to trans orientations of the phosphorus LP to
C(8) in the minor SP epimers (Table 2).
To estimate the steric demands of ligands 3aϪj, we calcu-
lated their Tolman’s angles[29] by the reported method, by
use of semiempirical quantum mechanical AM1 techniques
with full optimization of geometrical parameters.[30] The
obtained results (Table 1) show that the steric demands of
3aϪj vary over a rather wide range between 122° and 168°,
peaking at compounds 3g and 3f, bearing bulky menthyl or
adamantyl groups.
Scheme 1
In addition, new BINOL-based ligands 5a and 5b of
structural types La and Lb were obtained in order to com-
pare their effectiveness in Pd-catalysed allylation reactions
with ligands 3aϪj (Scheme 2).
The electronic demands of the novel ligands were deter-
mined from the 31P NMR and IR spectroscopic data
(Table 3) of their dimeric rhodium() chlorocarbonyl com-
plexes (Scheme 3).
The dimeric structures of complexes 6a؊c and 6i are sup-
ported by the intensive molecular ion peak m/z (%) ϭ 805
(40) [M]ϩ in the FAB mass spectrum of 6a. The IR spec-
trum of 6a contains a characteristic ν(RhϪCl) band at 273
Scheme 2
Compounds 3aϪj are stable on prolonged storage and, if cmϪ1, attributable to the bridging chloro ligand. Further
needed, can easily be purified either by vacuum distillation treatment of 6a with additional 3a gave the mononuclear
or by extraction with hexane. Since compound 1 is readily product 7 (Scheme 4).
available,[26] ligands 3aϪj can be prepared on multigram
The spectroscopic data for the rhodium chlorocarbonyl
scales.
complexes (Table 3) show that diamidophosphites 3aϪj lie
Eur. J. Org. Chem. 2004, 2214Ϫ2222
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V. N. Tsarev et al.
FULL PAPER
Table 2. 13C NMR spectroscopic data for ligands 3d and 3f, in CDCl3 (δC, JC,P, [Hz])
Carbon atom
CAr
Ligand
Carbon atom
CAr
Ligand
(RP)-3d
(SP)-3d
(RP)-3f
(SP)-3f
145.8 (2J ϭ 14.1)
128.6, 118.3
148.0 (2J ϭ 13.0)
128.1, 118.7
116.4 (3J ϭ 13.3)
72.6 (2J ϭ 5.7)
64.8 (2J ϭ 10.4)
50.6 (2J ϭ 6.6)
43.7 (2J ϭ 2.9)
31.7
145.7 (2J ϭ 14.5)
128.6, 118.2
115.3 (3J ϭ 12.1)
73.8 (2J ϭ 6.9)
62.3 (2J ϭ 7.6)
52.5 (2J ϭ 6.5)
47.7 (2J ϭ 35.5)
44.6 (2J ϭ 8.8)
35.9
147.5 (2J ϭ 13.2)
128.0, 118.8
116.6 (3J ϭ 13.3)
72.3 (2J ϭ 5.3)
65.0 (2J ϭ 10.6)
50.8 (2J ϭ 6.4)
44.1 (2J ϭ 3.4)
44.9 (2J ϭ 8.3)
35.8
115.5 (3J ϭ 12.5)
74.3 (2J ϭ 7.2)
64.5 (2J ϭ 8.0)
52.5 (2J ϭ 6.5)
47.8 (2J ϭ 35.5)
31.6
C (tBu)
5
4
8
1Ј
5
4
8
6
2Ј,8Ј,9Ј
4Ј,6Ј,10Ј
6
CH3(tBu)
7
30.7 (3J ϭ 8.4)
26.0 (3J ϭ 4.6)
30.6 (3J ϭ 7.6)
27.6
31.4
32.1
3Ј,5Ј,7Ј
7
30.7
30.6
27.7
25.9 (3J ϭ 4.6)
Both neutral and cationic palladium() complexes with
the new P*-monodentate ligands were prepared from
[Pd(allyl)Cl]2 (Scheme 5):
Table 3. Selected spectroscopic data for metal complexes 6aϪc, 6i,
8f, 8g, 9a and 9c-g (in CHCl3)
Complex
31P NMR, δP
IR, [cmϪ1
]
1
(RP)-6a
(RP)-6b
(RP)-6c
(RP)-6i
(RP)-8f
(SP)-8f
(RP)-8g
(RP)-9a
(RP)-9c
(RP)-9d
(SP)-9d
(RP)-9e
(SP)-9e
(RP)-9f
(SP)-9f
(RP)-9g
125.2, JP,Rh ϭ 250.5 Hz
2000[a]
1998[a]
2016[a]
1992[a]
268[c]
1
120.1, JP,Rh ϭ 250.4 Hz
1
130.3, JP,Rh ϭ 267.1 Hz
1
114.2, JP,Rh ϭ 222.5 Hz
111.3 (73%)[b]
98.9 (27%)
120.1 (52%), 119.5 (48%)[d]
118.9
270[c]
98.6 (66%), 95.5 (34%)[d]
106.2 (93%)[b]
89.4 (7%)
Scheme 5
107.5 (88%)[b]
84.6 (12%)
Their spectroscopic data are shown in Table 3. It should
be noted that, as a rule, the ratios of the P* epimers in the
palladium complexes were the same as in the free ligands
(Tables 1 and 3). The only exception is 9f, which contains
less minor epimer than the starting ligand 3f. According to
the 2JC(8),P values in the 13C NMR spectra of the complexes
(e.g., 8f and 9e, see Exp. Sect.), the major epimers have RP
configurations, analogously to the free ligands.
106.2 (97%)[b]
89.6 (3%)
113.0 (14%), 110.9 (86%)[d]
[a]
[b]
[c]
ν(CO) [cmϪ1].
Percentage of P* epimers. ν(Pd-Cl) [cmϪ1].
[d]
Percentage of exo and endo isomers.
Signals of both exo and endo isomers of 8g, 9c and 9g
are visible in their 31P NMR spectra (Table 3). This was not
the case for other palladium complexes, due either to fast
interconversion of the isomers or to the absence of one of
them (see ref.[34] and references cited therein). The IR
(Table 3),[35] 13C NMR (for the allyl ligand),[36] and MS
spectroscopic data (see Exp. Sect.) were also in a good
agreement with the proposed structures for 8f, 8g, 9a and
9c؊g.
Scheme 3
Scheme 4
The novel ligands were tested in the asymmetric Pd-cata-
lysed allylic substitution reactions with 1,3-diphenylallyl
acetate 10 as substrate (Scheme 6).
between phosphanes and phosphites in the spectrochemical
row of phosphorus ligands. Thus, the 1JP,Rh values for 6a؊c
1
and 6i are 70Ϫ80 Hz higher than the JP,Rh values for their
phosphane analogues[31] and 30Ϫ60 Hz lower than those
for the corresponding phosphites.[32,33] The increases both
1
in JP,Rh, from 222.5 to 267.1, and in ν(CO), from 1992 to
Scheme 6
2016 cmϪ1, in the sequence of complexes 6i؊6a, 6b؊6c re-
flects the increase in the π-acidity of the ligands in the
same direction.[32]
The results are given in Tables 4Ϫ6. Most of the ligands
showed good enantioselectivity (about 80% ee) in the allylic
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Eur. J. Org. Chem. 2004, 2214Ϫ2222

P-Chiral Monodentate Diamidophosphites
FULL PAPER
Table 4. Enantioselective allylic sulfonylation of 1,3-diphenylallyl
acetate with sodium p-toluenesulfinate
Table 5. Enantioselective allylic amination of 1,3-diphenylallyl acet-
ate with benzylamine
Entry Precatalyst
L
L/[Pd] Yield, [%] ee, [%]
Entry Precatalyst Solvent
L
θ, (°) L/[Pd] Yield, [%] ee, [%]
1
2
3
4
5
6
7
8
[Pd(allyl)Cl]2
[Pd(allyl)Cl]2
[Pd2(dba)3]·CHCl3 3a
9a
[Pd(allyl)Cl]2
[Pd(allyl)Cl]2
[Pd2(dba)3]·CHCl3 3b
[Pd(allyl)Cl]2
[Pd(allyl)Cl]2
[Pd2(dba)3]·CHCl3 3c
[Pd(allyl)Cl]2
[Pd2(dba)3]·CHCl3 3d
9d
[Pd(allyl)Cl]2
[Pd(allyl)Cl]2
3a
3a
1:1
2:1
1:1
2:1
1:1
2:1
1:1
1:1
2:1
1:1
1:1
1:1
2:1
1:1
2:1
1:1
2:1
1:1
1:1
2:1
1:1
2:1
1:1
1:1
2:1
1:1
2:1
1:1
2:1
1:1
1:1
2:1
1:1
1:1
2:1
1:1
1:1
2:1
1:1
17
16
37
98
72
80
53
28
30
23
32
16
44
83
97
23
20
27
35
53
45
50
22
27
92
47
27
16
16
15
17
18
17
21
21
28
35
0
83 (S)
81 (S)
78 (S)
64 (S)
84 (S)
80 (S)
80 (S)
13 (S)
44 (S)
13 (R)
94 (S)
80 (S)
97 (S)
79 (S)
86 (S)
78 (S)
85 (S)
83 (S)
30 (S)
90 (S)
83 (S)
78 (S)
80 (S)
76 (S)
78 (S)
78 (S)
73 (S)
15 (S)
13 (S)
1 (S)
1
2
3
4
5
6
7
8
[Pd(allyl)Cl]2 THF
[Pd(allyl)Cl]2 CH2Cl2 3a
9a CH2Cl2
[Pd(allyl)Cl]2 THF
[Pd(allyl)Cl]2 CH2Cl2 3b
[Pd(allyl)Cl]2 CH2Cl2 3b
3a 122 1:1
62
90
74
68
67
92
65
31
37
59
38
90
94
18
76
64
92
0
46 (R)
59 (R)
47 (R)
78 (R)
81 (R)
70 (R)
92 (R)
90 (R)
93 (R)
90 (R)
81 (R)
92 (R)
90 (R)
94 (R)
95 (R)
77 (R)
83 (R)
Ϫ
2:1
2:1
3b 134 1:1
3b
3b
1:1
2:1
[Pd(allyl)Cl]2 CH2Cl2 3c 152 2:1
[Pd(allyl)Cl]2 CH2Cl2 3d 156 2:1
3c
3c
9
9
9d
CH2Cl2
[Pd(allyl)Cl]2 THF
2:1
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
3e 137 1:1
3d
[Pd(allyl)Cl]2 CH2Cl2 3e
[Pd(allyl)Cl]2 CH2Cl2 3e
1:1
2:1
2:1
9e
CH2Cl2
3e
3e
[Pd(allyl)Cl]2 CH2Cl2 3f 168 2:1
9f
CH2Cl2
2:1
[Pd2(dba)3]·CHCl3 3e
[Pd(allyl)Cl]2 THF
3h 163 1:1
9e
[Pd(allyl)Cl]2 CH2Cl2 3h
2:1
[Pd(allyl)Cl]2
3f
[Pd(allyl)Cl]2 CH2Cl2 3i 137 2:1
[Pd2(dba)3]·CHCl3 3f
9f
[Pd(allyl)Cl]2
[Pd(allyl)Cl]2
[Pd2(dba)3]·CHCl3 3g
[Pd(allyl)Cl]2
[Pd(allyl)Cl]2
[Pd2(dba)3]·CHCl3 3h
9h
[Pd(allyl)Cl]2
[Pd(allyl)Cl]2
[Pd2(dba)3]·CHCl3 3i
[Pd(allyl)Cl]2
[Pd(allyl)Cl]2
[Pd2(dba)3]·CHCl3 3j
[Pd(allyl)Cl]2
[Pd(allyl)Cl]2
[Pd2(dba)3]·CHCl3 5a
[Pd(allyl)Cl]2
[Pd(allyl)Cl]2
[Pd2(dba)3]·CHCl3 5b
[Pd(allyl)Cl]2 THF 3j 149 1:1
18
0
0
51 (R)
Ϫ
Ϫ
[Pd(allyl)Cl]2 CH2Cl2 3j
[Pd(allyl)Cl]2 CH2Cl2 3j
1:1
2:1
1:1
1:1
2:1
1:1
1:1
2:1
3g
3g
[Pd(allyl)Cl]2 THF
5a
0
Ϫ
[Pd(allyl)Cl]2 CH2Cl2 5a
[Pd(allyl)Cl]2 CH2Cl2 5a
32
31
26
62
73
36 (R)
33 (R)
24 (R)
23 (R)
24 (R)
3h
3h
[Pd(allyl)Cl]2 THF
5b
[Pd(allyl)Cl]2 CH2Cl2 5b
[Pd(allyl)Cl]2 CH2Cl2 5b
3i
3i
3j
3j
61 (S)
59 (S)
9 (R)
72 (R)
70 (R)
63 (R)
46 (S)
Ϫ
Remarkably, in the allylic amination reaction, the ees of
11b roughly correlate with the steric demands of the ligand
expressed in terms of the cone angle θ (Table 5). The best
result (95% ee) was obtained with the bulkiest ligand 3f,
and even the most π-accepting diamidophosphite 3c did not
violate the correlation (Table 5, entry 7). The amide-type
ligands 3i and 3j appeared to be inefficient though, due to
miserable chemical yields. When THF was used as a solvent
instead of CH2Cl2 the results were substantially the same.
The general trends in allylic alkylation have much in com-
5a
5a
5b
5b
13
7 (S)
sulfonylation reaction (Table 4, ligands 3a, 3b, 3e, 3g, 3h).
Notably, the additional C*-stereogenic centres in the men- mon with the sulfonylation reaction discussed above. As in
thyl substituent of 3g did not provide any improvement. the sulfonylation, most of the ligands demonstrated good
Ligand 3f bearing a bulky adamantyl substituent gave up enantioselectivity (about 80% ee) in the alkylation of 1,3-
to 90% ee, while the best result (97% ee) was obtained with diphenylallyl acetate with dimethyl malonate (Table 6, li-
3d, which has an average θ value as high as 156° (Table 1). gands 3b, 3d؊f, 3h). Similarly, low conversion and moder-
It is important to note that all the efficient ligands men- ate optical yields of 11c were obtained with the ligands of
tioned have moderate π-acidity. Meanwhile, both more and marginal π-acidity (up to 66% ee with 3c, up to 62% ee with
less π-acidic ligands, such as 3c and 3i, respectively, pro- 3i). Application of [Pd2(dba)3]·CHCl3 as a precatalyst again
vided much lower chemical and especially optical yields. resulted mainly in reduction in the enantioselectivity. The
The ees did not exceed 44% for 3c and 15% for 3i. The main distinctive feature of the allylic alkylation is that the
notable increase in the enantioselectivity on going from 3i least bulky 3a provided the best stereoinduction (97% ee).
to 3j (up to 61%) is likely to be due to an increase in the θ
value from 137 to 149°. Nevertheless, the chemical yields cussed reactions are compounds with moderate π-acidity.
for both ligands were poor. They outperformed the BINOL-derived 5a and 5b, which
To summarize, the most efficient ligands in the three dis-
The use of [Pd2(dba)3]·CHCl3 instead of [Pd(allyl)Cl]2 as provided only moderate chemical and optical yields in the
the palladium precursor provided no essential advantages. Pd-catalysed allylic substitution reactions of 10 (Scheme 6,
Furthermore, notable reduction in enantioselectivity or Tables 4Ϫ6).
even an inversion of the absolute configuration of 11a was
Even more interesting is that the novel P*-monodentate
observed in some cases (Table 4, entries 10,12,30, and 33).
diamidophosphites were found to be superior stereoselec-
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V. N. Tsarev et al.
FULL PAPER
Table 6. Enantioselective allylic alkylation of 1,3-diphenylallyl acet-
ate with dimethyl malonate
Entry
Precatalyst
L
Conversion, [%]
ee, [%]
Scheme 7
1
[Pd(allyl)Cl]2
[Pd2(dba)3]·CHCl3
[Pd(allyl)Cl]2
[Pd2(dba)3]·CHCl3
[Pd(allyl)Cl]2
[Pd2(dba)3]·CHCl3
[Pd(allyl)Cl]2
[Pd2(dba)3]·CHCl3
[Pd(allyl)Cl]2
[Pd2(dba)3]·CHCl3
[Pd(allyl)Cl]2
[Pd2(dba)3]·CHCl3
[Pd(allyl)Cl]2
[Pd2(dba)3]·CHCl3
[Pd(allyl)Cl]2
[Pd2(dba)3]·CHCl3
[Pd(allyl)Cl]2
3a
3a
3b
3b
3c
3c
3d
3d
3e
3e
3f
98
65
16
92
29
9
35
9
62
45
28
4
82
90
20
10
1
2
8
97 (S)
94 (S)
70 (S)
77 (S)
55 (R)
66 (R)
82 (S)
36 (S)
78 (S)
80 (S)
86 (S)
32 (S)
78 (S)
74 (S)
62 (R)
55 (R)
31 (S)
9 (S)
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
Table 7. Enantioselective allylic alkylation of methyl (2-phenyl-
ortho-carboran-1-yl)phenyl acetate with methyl prop-2-enyl car-
bonate
Entry
Precatalyst
L
ee [%]
1
2
3
4
5
6
7
8
9
10
11
[Pd(allyl)Cl]2
9a
[Pd(allyl)Cl]2
[Pd(allyl)Cl]2
[Pd(allyl)Cl]2
9d
[Pd(allyl)Cl]2
[Pd(allyl)Cl]2
[Pd(allyl)Cl]2
[Pd(allyl)Cl]2
[Pd(allyl)Cl]2
3a
50
51
72
48
70
73
61
16
72
49
44
3b
3c
3d
3f
3h
3h
3i
3e
3f
3g
3h
3i
3i
3j
[Pd2(dba)3]·CHCl3
[Pd(allyl)Cl]2
[Pd2(dba)3]·CHCl3
[Pd(allyl)Cl]2
3j
5a
5a
5b
5b
9 (S)
3
20
58
22 (S)
60 (S)
52 (S)
[Pd2(dba)3]·CHCl3
carborane compound 12 and achieved enantioselectivities
of up to 73% ee (Scheme 7, Table 7).
Ligands 3b, 3d and 3g were found to be the most ef-
ficient. Notably, this is the first direct asymmetric reaction
in the carborane series. The obtained ees are fairly high for
this specific case of allylation reactions in which the arising
chiral centre is situated at the attacking nucleophile.[40]
Experimental Section
Figure 2. Well-known P*,N-bidentate diamidophosphite ligand
QUIPHOS
General Remarks: All reactions were carried out under dry argon
atmospheres. The solvents were dried before use according to the
methods described.[41] Methyl, isopropyl, tert-butyl and 1-methyl-
cyclobutyl alcohols were dried by heating at reflux over Mg/I2, fol-
lowed by distillation. Hexafluoroisopropyl alcohol was distilled
from over Na2SO4. Removal of moisture from phenol was achieved
by azeotropic distillation with benzene followed by distillation.
Adamantan-1-ol (Merck) and (1R,2S,5R)-(Ϫ)-menthol (Fluka)
tors to the well-known P*,N-bidentate ligand QUIPHOS
and its derivatives (Figure 2).
Specifically, while the ees of product 11b in the allylic
amination reaction were roughly equal (94% ee for
QUIPHOS[27] and 95% ee for 3f), in the allylic alkylation
reaction between 10 and dimethyl malonate, QUIPHOS
(85% ee[27]) and its analogues (R ϭ Me, Ph, tBu, CN, were sublimed at reduced pressure (1 Torr). Diethylamine, triethyl-
etc.[37]) were outplayed by 3a (97% ee). Therefore, removal
amine, pyrrolidine, piperidine and benzylamine were freshly dis-
tilled from over LiAlH4. Phosphorylating reagents 1 and 4 were
of the nitrogen donor centre and essential simplification of
the ligand structure resulted in increased enantioselectivity
and seem to represent a fruitful trend in chiral ligand de-
sign.
prepared by the reported methods,[26,42] as were the complexes
[Rh(CO)2Cl]2, [Pd(allyl)Cl]2 and [Pd2(dba)3]·CHCl3.[43Ϫ45] Both li-
gand 3d and complex 9d have been reported by us.[46] 1,3-Di-
phenylallyl acetate 10, methyl (2-phenyl-ortho-carboran-1-yl)phenyl
The synthetic availability and high efficiency of the P*-
acetate 12 and methyl prop-2-en-1-yl carbonate were prepared by
monodentate diamidophosphites make it feasible to con-
sider them promising ligands for catalytic processes of prac-
tical importance in, as one example, the Pd-catalysed asym-
the methods described earlier.[40,44,47] Sodium p-toluenesulfinate
(Acros Organics) was dried in vacuo (2 h, 80 °C, 1 Torr). N,O-Bis-
(trimethylsilyl)acetamide (BSA) and dimethyl malonate (Acros
metric alkylation step in the recently reported elegant syn- Organics) were used as received.
thesis of enantiomerically pure anti-inflammatory agent
IR spectra were recorded on Specord M-80 or Nicolet 750 devices
Ibuprofen.[38] Another possible field of their application is
the synthesis of chiral carborane derivatives. Carboranes
are objects of sustained interest as potential B-10 carriers
in Boron Neutron Capture Therapy (BNCT).[39] We tested
in CHCl3 (polyethylene cuvette) or in Nujol (CsI plates). 13C NMR
(100.61 MHz) and 31P NMR (161.98 MHz) spectra were measured
in CDCl3 on a Bruker AMX 400 device. 19F NMR (188.3 MHz)
spectra were measured in CDCl3 on a Bruker WP 200 SY instru-
ligands 3a؊i in the Pd-catalysed allylic alkylation of the ment. Chemical shifts (δ scale) are given in ppm relative to internal
2218  2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim www.eurjoc.org
Eur. J. Org. Chem. 2004, 2214Ϫ2222

P-Chiral Monodentate Diamidophosphites
FULL PAPER
CDCl3 (δ ϭ76.91 ppm for 13C NMR) or external 85% aqueous 280 Hz, CF3], 129.0 (s), 144.3 (d, 2J ϭ 16.4 Hz) (CAr) ppm. 19F
H3PO4 solution (δ ϭ0 ppm for 31P NMR) or CF3COOH (δ ϭ NMR (CDCl3): δF ϭ 4.1 (dq), 3.7 (dq) (4JF,F ϭ 7.5, 4JF,P ϭ 3.3 Hz)
0 ppm for 19F NMR). The 13C NMR peaks were ascribed by the ppm. MS (EI, 70 eV): m/z (%) ϭ 372 (44) [M]ϩ, 267 (55), 205 (32),
DEPT techniques. Mass spectra were recorded on Varian MAT-
311 (EI, 70 eV), AMD-402 FAB, or Finnigan LCQ electrospray
spectrometers. The analytical data were obtained in the Organic
Microanalysis Laboratory at the A. N. Nesmeyanov Institute of
Organoelement Compounds. The ees of 11aϪc and 13 were mea-
sured by HPLC on a Bruker LC 41 apparatus, with use of (R,R)-
WHELK-01 chiral columns for 11a and 13[48,49] and Daicel Chiral-
cel OD-H for 11b and 11c.[50]
116 (100). C14H15F6N2OP (372.0): calcd. C 45.17, H 4.06, N 7.53;
found C 44.98, H 4.27, N 7.24.
(2R,5S)-2-(1Ј-Methylcyclobutyl-1Ј)-3-phenyl-1,3-diaza-2-phospha-
bicyclo[3.3.0]octane (3e): Colourless oil, (1.12 g, 93%), b.p.
121Ϫ122°C (0.8 Torr). 13C NMR (CDCl3): δC ϭ 13.0 [s, C(3Ј)],
25.9 [d, 3J ϭ 4.6 Hz, C(7)], 26.7 [d, 3J ϭ 7.2 Hz, CH3], 31.6 [s,
C(6)], 36.1 [d, 3J ϭ 9.5 Hz, C(4Ј)], 36.9 [d, 3J ϭ 7.6 Hz, C(2Ј)], 47.9
2
2
2
[d, J ϭ 35.6 Hz, C(8)], 54.2 [d, J ϭ 6.9 Hz, C(4)], 62.5 [d, J ϭ
3
Preparation of the Ligands
8.0 Hz, C(5)], 75.7 [d, 2J ϭ 7.6 Hz, C(1Ј)], 115.3 (d, J ϭ 12.5 Hz),
118.4 (s), 128.6 (s), 145.3 (2J ϭ 14.5 Hz) (CAr) ppm. MS (EI,
70 eV): m/z (%) ϭ 290 (10) [M]ϩ, 221 (53), 205 (90), 116 (100).
C16H23N2OP (290.2): calcd. C 66.19, H 7.98, N 9.65; found C
65.97, H 7.76, N 9.32.
(2R,5S)-1,3-Diaza-2-chloro-3-phenyl-2-phosphabicyclo[3.3.0]octane
(1):
A solution of (S)-2-(anilinomethyl)-pyrrolidine (0.722 g,
4.1 mmol) in benzene (20 mL) was added dropwise at 0 °C over
15 min to a vigorously stirred solution of PCl3 (0.36 mL, 4.1 mmol)
and Et3N (1.12 mL, 8.2 mmol) in benzene (40 mL). The mixture
was then briefly heated to boiling point and cooled down to 20 °C.
(2R,5S)-2-(Tricyclo[3.3.1.1.3Ј,7Ј]dec-1Ј-yloxy)-3-phenyl-1,3-diaza-2-
phosphabicyclo[3.3.0]octane (3f): Colourless, viscous oil solidifying
Solid Et3N·HCl was filtered off, and the filtrate was concentrated on storage, (1.41 g, 95%), m.p. 61Ϫ62°C. MS (EI, 70 eV): m/z
in vacuo (40 Torr). The residue was dried for 30 min at 10 Torr and
distilled in vacuo (1 Torr). White crystalline powder (0.70 g, 71%),
(%) ϭ 356 (20) [M]ϩ, 221 (47), 205 (37), 135 (100). C21H29N2OP
(356.2): calcd. C 70.76, H 8.20, N 7.86; found C 70.49, H 8.42,
m.p. 110Ϫ111 °C, b.p. 156Ϫ158 °C (1 Torr). 13C NMR (CDCl3): N 7.57.
δC ϭ 27.48 [s, C(7)], 30.83 [s, C(6)], 44.08 [s, C(8)], 52.22 [s, C(4)],
(2R,5S,1ЈR,2ЈS,5ЈR)-2-(2Ј-Isopropyloxy-5Ј-methyl-cyclohex-1Ј-
65.97 [s, C(5)], 116.96Ϫ142.74 (CPh) ppm. 31P NMR (CDCl3), δP ϭ
yloxy)-3-phenyl-1,3-diaza-2-phosphabicyclo[3.3.0]octane (3g):
Colourless, very viscous oil, (1.4 g, 93%). 13C NMR (CDCl3): δC ϭ
15.1 [s, C(10Ј)], 21.0 [s, C(9Ј)], 22.1 [s, C(7Ј)], 22.7 [s, C(3Ј)], 24.9
153.66. MS (EI, 70 eV): m/z (%) ϭ 240 (56) [M]ϩ 205 (100) [M Ϫ
,
Cl]ϩ, 174 (12) [M Ϫ PCl]ϩ. C11H14ClN2P (240.0): calcd. C 54.90,
H 5.86, N 11.64; found C 55.27, H 5.58, N 11.95.
3
[s, C(8Ј)], 26.1 [d, J ϭ 3.8 Hz, C(7)], 31.7 [s, C(6)], 31.8 [s, C(5Ј)],
2
General Procedure for Preparation of 3aϪj: A solution of Et3N
(0.6 mL, 4.2 mmol) and the relevant alcohol or amine (4.2 mmol)
in benzene (10 mL) was added dropwise at 0 °C over 15 min to a
vigorously stirred solution of 1 (1 g, 4.2 mmol) in benzene (10 mL).
The mixture was then briefly heated to boiling point and allowed
to cool to 20 °C. Solid Et3N·HCl was filtered off, and the filtrate
was concentrated in vacuo (40 Torr) at 50 °C. Products 3aϪe and
3i were distilled in vacuo. Products 3fϪh and 3j were extracted
with hexane.
34.2 [s, C(4Ј)], 43.7 [s, C(6Ј)], 48.5 [d, J ϭ 36.2 Hz, C(8)], 48.8 [d,
3J ϭ 1.9 Hz, C(2Ј)], 54.3 [d, 2J ϭ 6.9 Hz, C(4)], 62.6 [d, 2J ϭ
3
8.4 Hz, C(5)], 74.2 [d, 2J ϭ 9.2 Hz, C(1Ј)], 114.9 (d, J ϭ 13.3 Hz),
118.4 (s), 128.7 (s), 145.7 (d, 2J ϭ 15.3 Hz) (CAr) ppm. MS (EI,
70 eV): m/z (%) ϭ 360 (10) [M]ϩ, 221 (73), 205 (59), 116 (100).
C21H33N2OP (360.2): calcd. C 69.97, H 9.23, N 7.77; found C
69.58, H 8.96, N 7.41.
(2R,5S)-2-Phenoxy-3-phenyl-1,3-diaza-2-phosphabicyclo[3.3.0]-
octane (3h): White solid, (1.15 g, 93%), m.p. 94Ϫ95°C. 13C NMR
3
(2R,5S)-1,3-Diaza-2-methoxy-3-phenyl-2-phosphabicyclo[3.3.0]- (CDCl3): δC ϭ 26.2 [d, J ϭ 4.2 Hz, C(7)], 31.2 [s, C(6)], 47.6 [d,
octane (3a): Colourless oil, (0.9 g, 92%), b.p. 81Ϫ82 °C (0.8 Torr).
2J ϭ 35.1 Hz, C(8)], 53.7 [d, 2J ϭ 7.6 Hz, C(4)], 62.5 [d, 2J ϭ
13C NMR (CDCl3): δC ϭ 25.8 [d, 3J ϭ 3.4 Hz, C(7)], 31.8 [s, C(6)], 8.8 Hz, C(5)], 114.9Ϫ153.4 (CAr) ppm. MS (EI, 70 eV): m/z (%) ϭ
48.3 [d, 2J ϭ 38.9 Hz, C(8)], 48.6 (s, CH3), 54.7 [d, 2J ϭ 6.9 Hz, 298 (10) [M]ϩ, 205 (100), 136 (78). C17H19N2OP (298.1): calcd. C
C(4)], 63.0 [d, 2J ϭ 8.8 Hz, C(5)], 114.4 (d, 3J ϭ 11.8 Hz), 118.5
68.44, H 6.42, N 9.39; found C 68.16, H 6.57, N 9.62.
2
(s), 128.7 (s), 145.3 (d, J ϭ 15.7 Hz) (CAr) ppm. MS (EI, 70 eV):
(2R,5S)-2-Diethylamino-3-phenyl-1,3-diaza-2-phosphabicyclo[3.3.0]-
octane (3i): Colourless, viscous oil, solidifying on storage, (1.0 g,
90%), b.p. 118Ϫ119°C (0.8 Torr), m.p. 38Ϫ39°C. 13C NMR
m/z (%)
ϭ
236 (44) [M]ϩ, 205 (45), 131 (100), 116 (95).
C12H17N2OP (236.1): calcd. C 61.01, H 7.25, N 11.86; found C
61.22, H 7.37, N 11.52.
3
(CDCl3): δC ϭ 14.6 (d, J ϭ 2.7 Hz, CH3), 25.4 [d, 3J ϭ 3.8 Hz,
(2R,5S)-2-Isopropyloxy-3-phenyl-1,3-diaza-2-phosphabicyclo[3.3.0]-
octane (3b): Colourless oil, (0.9 g, 82%), b.p. 76Ϫ77°C (0.8 Torr).
C(7)], 32.3 [s, C(6)], 39.5 [d, 2J ϭ 18.7 Hz, NCH2], 49.6 [d, 2J ϭ
41.2 Hz, C(8)], 53.9 [d, 2J ϭ 5.7 Hz, C(4)], 61.8 [d, 2J ϭ 7.6 Hz,
3
2
13C NMR (CDCl3): δC ϭ 24.2 (s, CH3), 24.6 (s, CH3), 26.0 [d, 3J ϭ C(5)], 114.6 (d, J ϭ 12.1 Hz), 117.2 (s), 128.5 (s), 146.5 (d, J ϭ
4.2 Hz, C(7)], 31.8 [s, C(6)], 48.1 [d, 2J ϭ 37.8 Hz, C(8)], 54.0 [d, 14.5 Hz) (CAr) ppm. MS (EI, 70 eV): m/z (%) ϭ 277 (8) [M]ϩ, 221
3
2J ϭ 7.2 Hz, C(4)], 62.6 [d, J ϭ 8.8 Hz, C(5)], 66.1 (s, CH), 114.7 (23), 205 (52), 58 (100). C15H24N3P (293.2): calcd. C 64.96, H 8.72,
(d, 3J ϭ 11.8 Hz), 118.4 (s), 128.7 (s), 145.6 (d, 2J ϭ 16.0 Hz) (CAr
)
N 15.15; found C 65.17, H 8.63, N 14.93.
ppm. MS (EI, 70 eV): m/z (%) ϭ 264 (87) [M]ϩ, 221 (68), 205 (72),
116 (100). C14H21N2OP (264.1): calcd. C 63.62, H 8.01, N 10.60;
found C 63.31, H 8.24, N 10.37.
(2R,5S)-2-Piperidino-3-phenyl-1,3-diaza-2-phosphabicyclo[3.3.0]-
octane (3j): Colourless oil, (1.1 g, 88%). 13C NMR (CDCl3): δC
ϭ
24.9 (s, CH2), 25.4 [d, 3J ϭ 3.8 Hz, C(7)], 26.7 [d, 3J ϭ 5.0 Hz,
(2R,5S)-2-(Hexafluoroisopropyloxy)-3-phenyl-1,3-diaza-2-phos- CH2], 32.1 [s, C(6)], 45.7 [d, 2J ϭ 15.6 Hz, NCH2], 50.0 [d, 2J ϭ
phabicyclo[3.3.0]octane (3c): Colourless oil, (1.25 g, 81%), b.p.
40.1 Hz, C(8)], 54.1 [d, 2J ϭ 5.3 Hz, C(4)], 62.2 [d, 2J ϭ 7.6 Hz,
3
2
92Ϫ93°C (0.8 Torr). 13C NMR (CDCl3): δC ϭ 26.4 [d, 3J ϭ 4.5 Hz,
C(5)], 114.6 (d, J ϭ 11.8 Hz), 117.3 (s), 128.6 (s), 145.6 (d, J ϭ
C(7)], 31.7 [s, C(6)], 47.3 [d, 2J ϭ 34.3 Hz, C(8)], 53.4 [d, 2J ϭ 13.7 Hz) (CAr) ppm. MS (EI, 70 eV): m/z (%) ϭ 289 (55) [M]ϩ, 205
7.2 Hz, C(4)], 63.0 [d, 2J ϭ 8.1 Hz, C(5)], 68.9 (qt, 2J ϭ 3.6, 2JC,F ϭ (100), 136 (81), 84 (78). C16H24N3P (305.2): calcd. C 66.41, H 8.36,
3
1
33.2 Hz, CH), 115.3 (d, J ϭ 12.9 Hz), 120.0 (s), 121.5 [q, JC,F
ϭ
N 14.52; found C 66.23, H 8.52, N 14.66.
Eur. J. Org. Chem. 2004, 2214Ϫ2222
www.eurjoc.org
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
2219

V. N. Tsarev et al.
FULL PAPER
General Procedure for Preparation of 5a and 5b: A solution of Et3N
(0.2 mL, 1.4 mmol) and the relevant alcohol or amine (1.4 mmol)
in toluene (7 mL) was added dropwise at 0 °C over 15 min to a
vigorously stirred solution of 4 (0.5 g, 1.4 mmol) in toluene (7 mL).
The mixture was then briefly heated to boiling point and allowed
to cool to 20 °C. Solid Et3N·HCl was filtered off, and hexane
(15 mL) was added to the filtrate. The resulting mixture was fil-
tered, the solvent was evaporated at reduced pressure (40 Torr), and
the product was dried in vacuo (1 Torr) for 2 h.
[Pd(allyl)(3g)Cl] (8g): Yellow-orange powder, (0.19 g, 89%), m.p.
176Ϫ178 °C (dec.). MS (FAB): m/z (%) ϭ 543 (5) [M]ϩ, 508 (8) [M
Ϫ Cl]ϩ, 467 (27), 116 (100). C24H38ClN2OPPd (542.1): calcd. C
53.05, H 7.05, N 5.16; found C 53.34, H 6.73, N 5.44.
General Procedure for Preparation of Pd Complexes 9a and 9c؊g:
A solution of the relevant ligand (0.8 mmol) in CHCl3 (15 mL)
was added dropwise over 40 min to a vigorously stirred solution of
[Pd(allyl)Cl]2 (0.073 g, 0.20 mmol) in CHCl3 (15 mL). The mixture
was stirred for an additional 1 h, followed by dropwise addition of
(Rax)-2-(1Ј-Methylcyclobut-1Ј-yloxy)-dinaphtho[2,1-d:1Ј,2Ј-f][1,3,2]- AgBF4 (0.078 g, 0.4 mmol) in THF (15 mL) over 20 min. The mix-
dioxaphosphepine (5a): Colourless tar, (0.55 g, 97%). 13C NMR
ture was stirred for 1 h, and precipitated AgCl was filtered off. The
(CDCl3): δC ϭ 13.2 [s, C(3Ј)], 27.4 (d, J ϭ 6.9 Hz, CH3), 36.8 [d, filtrate was concentrated at reduced pressure to the volume of ca.
0.5 mL, and diethyl ether (15 mL) was added. The precipitated
solid was separated by centrifugation, washed with diethyl ether (2
153.1 ppm. MS (EI, 70 eV): m/z (%) ϭ 400 (41) [M]ϩ, 332 (97), 268 ϫ 10 mL) and dried in vacuo (1 Torr) for 1 h.
3
3J ϭ 6.9 Hz, C(4Ј)], 36.9 [d, 3J ϭ 6.1 Hz, C(2Ј)], 78.5 [d, 2J ϭ
14.1 Hz, C(1Ј)], 121.7Ϫ147.6 (CAr) ppm. 31P NMR (CDCl3): δP
ϭ
(98), 239 (100). C25H21O3P (400.1): calcd. C 74.99, H 5.29; found
C 75.18, H 5.07.
[Pd(allyl)(3a)2]؉ BF4 (9a): White powder, (0.27 g, 95%), m.p.
Ϫ
178Ϫ180 °C (dec.). MS (FAB): m/z (%) ϭ 619 (91) [M Ϫ BF4]ϩ,
578 (63), 131 (100). C27H39BF4N4O2P2Pd (706.2): calcd. C 45.88,
H 5.56, N 7.93; found C 45.52, H 5.21, N 8.11.
(Rax)-2-(3-Pyrrolidin-1Ј-yl)-dinaphtho[2,1-d:1Ј,2Ј-f][1,3,2]dioxaphos-
phepine (5b): White solid, (0.52 g, 95%), m.p. 119Ϫ120°C. 13C
NMR (CDCl3): δC ϭ 25.6 (d, 3J ϭ 4.2 Hz, CH2), 45.4 (d, 2J ϭ
16.0 Hz, NCH2), 121.2Ϫ150.1 (CAr) ppm. 31P NMR (CDCl3): δP ϭ
150.7 ppm. MS (EI, 70 eV): m/z (%) ϭ 385 (48) [M]ϩ, 315 (64), 268
(72), 70 (100). C24H20NO2P (385.1): calcd. C 74.80, H 5.23, N 3.63;
found C 74.62, H 4.99, N 3.35.
[Pd(allyl)(3c)2]؉ BF4 (9c): Brown powder, (0.35 g, 90%), m.p.
Ϫ
177Ϫ179 °C (dec.). MS (FAB): m/z (%) ϭ 891 (82) [M Ϫ BF4]ϩ,
850 (54), 116 (100). C31H35BF16N4O2P2Pd (978.1): calcd. C 38.04,
H 3.60, N 5.72; found C 38.30, H 3.29, N 5.57.
Ϫ
[Pd(allyl)(3e)2]؉ BF4 (9e): Yellow powder, (0.32 g, 96%), m.p.
Preparation of the Complexes
166Ϫ168 °C (dec.). 13C NMR (CDCl3): δC ϭ 13.4 [s, C(3Ј)], 25.5
[s, C(7)], 27.1 (s, CH3), 31.8 [s, C(6)], 36.2 [s, C(4Ј)], 37.1 [s, C(2Ј)],
General Procedure for Preparation of Rh Complexes 6a؊c, 6i and
7: Rhodium() chlorocarbonyl complexes with ligands 3a؊c and 3i
were prepared for 31P NMR, IR, and FAB mass spectral experi-
ments as follows. A solution of the relevant ligand (0.18 mmol) in
CHCl3 (1.5 mL) was added dropwise over 20 min to a vigorously
stirred solution of [Rh(CO)2Cl]2 (0.035 g, 0.09 mmol) in CHCl3
(1.5 mL). An aliquot portion of the solution (1 mL) was used for
the appropriate experiment.
2
2
48.2 [d, J ϭ 23.6 Hz, C(8)], 53.5 [d, J ϭ 24.4 Hz, C(4)], 60.8 [s,
C(5)], 70.1 [t, 2J ϭ 52.7 Hz, CH2(allyl)], 82.2 [s, C(1Ј)], 115.8 (d, 3J ϭ
2
14.4 Hz), 120.6 (s), 123.6 (t, J ϭ 8.4 Hz, CHallyl), 129.2 (s), 142.7
2
(d, J ϭ 11.3 Hz) (CAr) ppm. MS (ESI): m/z (%) ϭ 727 (25) [M Ϫ
BF4]ϩ, 437 (100), 174 (14). C35H51BF4N4O2P2Pd (814.3): calcd. C
51.58, H 6.31, N 6.87; found C 51.32, H 6.52, N 6.68.
[Pd(allyl)(3f)2]؉ BF4Ϫ (9f): Light brown powder, (0.33 g, 88%), m.p.
189Ϫ191 °C (dec.). MS (FAB): m/z (%) ϭ 859 (89) [M Ϫ BF4]ϩ,
818 (50), 135 (100). C45H63BF4N4O2P2Pd (946.4): calcd. C 57.06,
H 6.70, N 5.92; found C 56.82, H 6.52, N 5.81.
Complex 7 was prepared similarly, by starting from ligand 3a
(0.36 mmol) in a CHCl3 solution.
General Procedure for Preparation of Pd Complexes 8f and 8g: A
solution of the relevant ligand (0.4 mmol) in CHCl3 (15 mL) was
added dropwise over 40 min to a vigorously stirred solution of
[Pd(allyl)Cl]2 (0.073 g, 0.20 mmol) in CHCl3 (15 mL). The mixture
was stirred for an additional 1 h and the solvent was evaporated at
reduced pressure (40 Torr). The residue was washed with diethyl
ether (2 ϫ 10 mL) and dried in vacuo (1 Torr) for 1 h.
[Pd(allyl)(3g)2]؉ BF4 (9g): White powder, (0.34 g, 90%), m.p.
Ϫ
173Ϫ175 °C (dec.). MS (FAB): m/z (%) ϭ 867 (94) [M Ϫ BF4]ϩ,
826 (48), 205 (100). C45H71BF4N4O2P2Pd (954.4): calcd. C 56.58,
H 7.49, N 5.87; found C 56.31, H 7.20, N 6.11.
Catalytic Experiments
Palladium-Catalysed Allylic Sulfonylation of 1,3-Diphenylallyl Ace-
tate with Sodium p-Toluenesulfinate: A solution of [Pd(allyl)Cl]2
(0.0037 g, 0.01 mmol) or [Pd2(dba)3]·CHCl3 (0.0103 g, 0.01 mmol)
and the appropriate ligand (0.02Ϫ0.04 mmol) in THF (5 mL) was
stirred for 40 min [alternatively, the presynthesized appropriate
complex (0.02 mmol) was dissolved in THF (5 mL)]. 1,3-Di-
phenylallyl acetate 10 (0.1 mL, 0.5 mmol) was added to the solution
and the reaction mixture was stirred for 15 min. Sodium p-toluene-
sulfinate (0.178 g, 1.00 mmol) was added, and the reaction mixture
was stirred for 48 h, quenched with brine (10 mL) and extracted
with THF (3 ϫ 7 mL). The organic layer was washed with brine (2
ϫ 7 mL) and dried over MgSO4. The solvent was evaporated at
reduced pressure (40 Torr). Crystallization of the residue from
EtOH, followed by desiccation in vacuo (10 Torr, 12 h), gave the
product 11a as white crystals. All spectroscopic data for compound
11a were in good agreement with the literature.[48]
[Pd(allyl)(3f)Cl] (8f): Light brown powder, (0.20 g, 92%), m.p.
165Ϫ167 °C (dec.), 13C NMR (CDCl3): δC ϭ 26.9 [d, 3J ϭ 5.7 Hz,
3
C(7)], 30.9 [s, C(3Ј), C(5Ј), C(7Ј)], 31.6 [d, J ϭ 1.9 Hz, C(6)], 35.7
3
[s, C(4Ј), C(6Ј), C(10Ј)], 43.9 [d, J ϭ 5.0 Hz, C(2Ј), C(8Ј), C(9Ј)],
47.4 [d, 2J ϭ 23.3 Hz, C(8)], 54.2 [s, C(4)], 60.5 [s, C(5)], 61.7 [s,
CH2(allyl, trans-Cl)], 77.9 [d, 2J ϭ 46.9 Hz, CH2(allyl, trans-P)], 82.4 [d,
2J ϭ 20.6 Hz, C(1Ј)], 115.7 (d, 3J ϭ 8.0 Hz), 117.5 (d, 2J ϭ 9.5 Hz,
CHallyl), 119.7 (s), 128.5 (s), 143.9 (d, 2J ϭ 12.6 Hz) (CAr) [for (RP)-
8f] ppm. 13C NMR (CDCl3): δC ϭ 27.4 [d, 3J ϭ 4.9 Hz, C(7)], 31.2
[s, C(3Ј), C(5Ј), C(7Ј)], 31.5 [d, 3J ϭ 1.5 Hz, C(6)], 35.4 [s, C(4Ј),
C(6Ј), C(10Ј)], 44.2 [d, 3J ϭ 4.6 Hz, C(2Ј), C(8Ј), C(9Ј)], 50.2 [s,
C(8)], 55.7 [d, 2J ϭ 6.5 Hz, C(4)], 59.8 [s, CH2(allyl, trans-Cl)], 63.0 [d,
2J ϭ 1.9 Hz, C(5)], 78.4 [d, 2J ϭ 44.2 Hz, CH2(allyl, trans-P)], 81.4 [d,
2J ϭ 17.4 Hz, C(1Ј)], 117.7 (d, 2J ϭ 7.6 Hz, CHallyl), 118.1 (d, 3J ϭ
2
9.5 Hz), 121.0 (s), 128.7 (s), 145.4 (d, J ϭ 8.2 Hz) (CAr) [for (SP)-
8f] ppm. MS (FAB): m/z (%) ϭ 539 (3) [M]ϩ, 503 (10) [M Ϫ Cl]ϩ,
462 (14), 135 (100). C24H34ClN2OPPd (538.1): calcd. C 53.44, H Palladium-Catalysed Allylic Amination of 1,3-Diphenylallyl Acetate
6.35, N 5.19; found C 53.29, H 6.52, N 5.52.
2220
with Benzylamine:
A
solution of [Pd(allyl)Cl]2 (0.0037 g,
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
Eur. J. Org. Chem. 2004, 2214Ϫ2222

P-Chiral Monodentate Diamidophosphites
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0.01 mmol) and the appropriate ligand (0.02Ϫ0.04 mmol) in THF
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