Resolution of the atropochiral biminap ligand and applications in asymmetric catalysis

Article abstract of DOI:10.1002/asia.200900663

Enantiomeric resolution of the rac-biminap ligand is achieved through fractional crystallization of four diastereoisomeric palladium complexes involving ortho-metallated enantiomerically pure (R)-dimethyl(1-naphthylethyl) amine as a chiral auxiliary. Afte

Full text of DOI:10.1002/asia.200900663

DOI: 10.1002/asia.200900663
Resolution of the Atropochiral Biminap Ligand and Applications in
Asymmetric Catalysis
[
a, b]
[a, b]
[a, b]
[a, b]
Ibrahim Abdellah,
Nathalie Debono,
Yves Canac,*
Laure Vendier,
and
[
a, b]
Remi Chauvin*
Abstract: Enantiomeric resolution of
the rac-biminap ligand is achieved
through fractional crystallization of
four diastereoisomeric palladium com-
plexes involving ortho-metallated enan-
tiomerically pure (R)-dimethyl(1-naph-
thylethyl)amine as a chiral auxiliary.
After decomplexation, the absolute
configuration of (R)-biminap and (S)-
biminap has been unambiguously at-
tributed by single-crystal X-ray crystal-
lography, and their stereochemical
purity is confirmed by measurement of
their optical rotation and by re-deriva-
tization with the initial resolving chiral
complex. Palladium complexes of bimi-
nap are shown to efficiently catalyze
Tsuji–Trost allylic substitution of 3-ace-
toxy-1,3-diphenylpropene by sodium
dimethyl malonate. In the asymmetric
version using the enantiomerically pure
(R)-biminap ligand, significant solvent
and anion effects are evident, and an
ee up to 90% is obtained.
Keywords: allylic compounds
·
asymmetric catalysis · chiral auxila-
ries · enantioselectivity · palladium
Introduction
much more electron-poor than the corresponding binap
[5]
ligand and specific applications in asymmetric catalysis
[4]
The N,N’-disubstituted imidazole core is the p-electron do-
nating source for the strongly s-donating N-heterocyclic car-
bene (NHCs) ligands, which have numerous applications in
catalytic processes requiring electron-rich transition metal
centers (e.g., where oxidative addition is a limiting step of
the catalytic cycle). In contrast, the N-monosubstituted
imidazole core is the s-electron withdrawing group of the
weakly s-donating imidazolylphosphines. Within the catego-
have been envisaged. Nevertheless, a single type of ligand
with extreme (strong or weak) donating character is rarely
sufficient because the transition metal center must satisfy
several criteria for achieving selectivity and activity over all
the catalytic steps. This is illustrated by the second genera-
tion Grubbs Ru catalyst for alkene metathesis, where the
effect of the highly electron-rich NHC ligand is balanced by
that of a PCy3 ligand. In the chiral chelating version
(Scheme 1), beyond Achiwaꢀs early Rh-bcpm catalysts for
asymmetric hydrogenation of ketones (where the electron-
[1]
[6]
[
2]
ry of chiral C -symmetric biaryl ligands, and more specifi-
2
[3]
cally, of bisheteroaryl ligands, Sannicoloꢀs 2,2’-bis(diphe-
nylphosphino)-1,1’-bisbenzimidazole (bimip) ligand was
claimed to be the most electron-poor ligand amongst the
rich dicyclohexylphosphine end is balanced by a PPh
2
[7]
end), one may cite Takayaꢀs atropochiral Rh-binaphos cat-
alyst for asymmetric hydroformylation (where the electron-
[4]
five-membered bisheteroaromatic diphosphanes. Bimip is
[8]
poor phosphite end is balanced by a napht-PPh end), and
2
the Chanꢀs recent Pd-Imidazolylphosphine-thioether cata-
[
a] I. Abdellah, Dr. N. Debono, Dr. Y. Canac, Dr. L. Vendier,
Prof. R. Chauvin
CNRS
LCC (Laboratoire de Chimie de Coordination)
2
05, route de Narbonne, F-31077 Toulouse (France)
Fax : (+33)5-61-55-30-03
E-mail: yves.canac@lcc-toulouse.fr
chauvin@lcc-toulouse.fr
[
b] I. Abdellah, Dr. N. Debono, Dr. Y. Canac, Dr. L. Vendier,
Prof. R. Chauvin
Universitꢁ de Toulouse
UPS, INP
1
Scheme 1. Examples of C -symmetric chiral chelating diphosphane li-
LCC
gands, with either electron-rich or electron-poor dominant P-coordinating
character.
F-31077 Toulouse (France)
Chem. Asian J. 2010, 5, 1225 – 1231
ꢂ 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
1225

FULL PAPERS
lysts for Tsuji–Trost allylation (where the electron-poor imi-
descriptor corresponds to the configuration of the atropo-
stereogenic naphthyl-benzimidazolyl bond (Scheme 2). This
assignment is partly confirmed by X-ray diffraction analysis.
Yellow single crystals deposited from a CH Cl /Et O solu-
[9]
dazolylphosphine end is balanced by a Fc-SR end). In the
same vein, the atropochiral biminap ligand 1 has been de-
vised as a bimip/binap hybrid, where the electron-poor imi-
2
2
2
[10]
dazolyphosphine end is balanced by a napht-PPh end.
tion of 3a–d were submitted to an X-ray diffraction analysis
2
[15]
The biminap ligand has been synthesized in the racemic
series, and its moderately weak donating character was illus-
(Figure 1). As proposed above, the obtained (R)-cis con-
trated to be valuable for the catalytic activity of a Cl Pd-bi-
2
minap complex in the Sonogashira-type coupling of alkynes
with acyl chlorides (where the Lewis acidity of the metal is
[10]
the determining factor).
The remaining challenges are:
(
i) the enantiomeric resolution of rac-biminap 1, and (ii) the
investigation of the performance of a pure enantiomer in
asymmetric catalysis. For the former, the selected resolving
tool is based on the use of a chiral arylethylamine ortho-pal-
ladated complex, which proved efficient for atropochiral P,P
[11]
and P,N ligands, and which was recently successfully ap-
[12]
plied in the isostructural NHC-ylide series. For the latter
challenge, the Tsuji–Trost catalytic allylation of malonates is
[13]
selected as a suitable paradigm of asymmetric catalysis:
electron-deficient diphosphane ligands are indeed expected
II
to enhance the electrophilicity of the p-allyl-Pd intermedi-
ate.
Figure 1. ORTEP view of the X-ray crystal structure of the (R)-cis stereo-
isomer 3b, with thermal ellipsoids drawn at the 30% probability level
(for clarity, the hexafluorophosphate anion and H atoms are omitted).
Results and Discussion
Optical Resolution of rac-Biminap 1
Amongst classical N,N-dimethyl(1-arylethyl)amine resolving
agents, the (R)-a-naphthyl derivative was selected (prelimi-
nary attempts at using the (R)-phenyl derivative indeed pro-
duced intractable mixtures). The palladium complex (R)-2
figuration was tentatively assigned to the 3b isomer (defined
by its NMR signature). The Pd atom is located at the
II
center of a quasi-square planar environment, where the ni-
trogen atom lies in the cis-position with respect to the ben-
zymidazolyl-PPh2 moiety (P1-Pd1-C43=158.46(15)8; P2-
Pd1-N3=155.81(14)8). The seven-membered palladacycle is
boat-shaped, with the bow occupied by a phosphorus atom
and the stern by the CꢀC bond of the naphthyl moiety. X-
[14]
was thus prepared according to the described procedure.
Half an equivalent of (R)-2 was added to a solution of rac-
[10]
biminap 1 in CH Cl .
After metathesis of the chloride
2
2
anion by addition of an aqueous solution of ammonium hex-
afluorophosphate in MeOH, a mixture of four complexes
3
a–d was obtained in 96% overall yield (Scheme 2).
The P NMR spectrum of the mixture exhibited four AB
ray diffraction data of 3b also indicate that coordination of
biminap 1 induces a decrease in the C10-C9-N2-C1 dihedral
angle (3b: 70.378; 1: 75.668), as previously observed in the
31
systems in the typical range for Pd-diphosphane complexes.
Assuming that the absolute configuration (R) of the carbon
atom of the N,N-dimethyl(1-a-naphthylethyl)amine ligand is
stable, the four sets of signals were tentatively assigned to
the enantiomerically pure diastereoisomers (R)-trans (3a,
dP =26.33, 8.42 ppm, d, JPP =47.4 Hz; 10%), (R)-cis (3b,
dP =37.65, 4.05 ppm; d, JPP =46.3 Hz; 40%), (S)-trans (3c,
dP =21.41, 8.88 ppm, d, JPP =41.2 Hz; 22%), and (S)-cis (3d,
dP =33.86, 2.43 ppm, d, JPP =40.2 Hz; 28%), where the CIP
[10]
analoguous PdCl complex.
2
After evaporation of the mother liquor, the diastereoiso-
mers 3a–d could then be separated, two-by-two, by fraction-
al crystallization. After enrichment from a concentrated
CH Cl /Et O solution at room temperature, recrystallization
2
2
2
from the same solvent mixture of the deposited solid (3a–b/
3c–d: 90:10) afforded yellow crystals of 3a (20%) and 3b
(80%) in 42% yield, where the percentages were estimated
3
1
by
P NMR analysis. The
mother liquor (enriched in the
most soluble diastereoisomers
3
c–d) was then evaporated to
dryness, and the solid residue
was recrystallized from
CH Cl /pentane mixture at
a
2
2
room temperature. Weighting
and P NMR analysis of the
Scheme 2. Preparation of a four-component diastereoisomeric mixture of the cationic palladium complexes
3
1
3
a–d from rac-biminap 1.
1226
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ꢂ 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Asian J. 2010, 5, 1225 – 1231

Resolution of the Atropochiral Biminap Ligand
deposited yellow solid indicated the exclusive presence of
diastereoisomers 3c (60%) and 3d (40%) in 40% overall
yield.
At this stage, the homochirality of the biminap ligands in
each pair of stereoisomeric mixtures 3a–3b and 3c–3d re-
mained to be checked. Assuming the (R)-cis stereochemical
assignment for 3b (corresponding to the X-ray diffraction
data; Figure 1), the homochiral situation would confirm the
(
R)-trans assignment for 3a, and the (S)-trans and (S)-cis
global assignment for 3c and 3d.
Decomplexation of biminap 1 from the two isolated pairs
of diastereoisomers 3a–b and 3c–d was thus classically ach-
ieved by treatment with 1,2-bis(diphenylphosphino)ethane
in CH Cl at room temperature. While the ligand exchange
2
2
from 3a–b was accomplished in 3 h affording 1a in 76%
yield, the same reaction from 3c–d required 3 days to give
1
1
1
b in 81% yield. As expected, the released ligands 1a and
3
1
b exhibited the same P NMR resonances as rac-biminap
[10]
(d =ꢀ18.10, ꢀ26.69 ppm; d, J =32.8 Hz).
The struc-
P
PP
ture of the diphosphanes 1a and 1b was then determined by
X-ray diffraction analysis of colorless single crystals deposit-
ed from a CH Cl /pentane mixture at room temperature
2
2
[15]
(
Figure 2, Table 1).
The absolute configuration of 1a and 1b was thus as-
cribed to (R) [Flack parameter: ꢀ0.03(4)] and (S) [Flack pa-
rameter: +0.01(4)], respectively. The enantiomeric purity of
diphosphanes 1a and 1b was then supported by the mea-
2
3
surement of opposite optical rotation values: (R)-1a: ½aꢁ =
D
2
D
3
+
10.88; (S)-1b: ½aꢁ =ꢀ10.68. It was confirmed by derivati-
zation using the chiral palladium complex (R)-2, complexa-
tion of each enantiomers 1a and 1b quantitatively afforded
the corresponding original pairs of diastereoisomers 3a–b
and 3c–d, respectively. These results show that the absolute
configuration of the naphthyl-benzymidazolyl core (R or S)
is the determining factor controlling the solubility and crys-
tallinity of the four diastereoisomers 3a–d.
Figure 2. ORTEP views of the X-ray crystal structures of the resolved bi-
minap enantiomers (R)-1a (left) and (S)-1b (right), with thermal ellip-
soids drawn at the 30% probability level (for clarity, H atoms are omit-
ted).
Table 1. Selected crystallographic structural data of rac-biminap 1 and bi-
minap enantiomers (R)-1a, (S)-1b (Figure 2): bond lengths in ꢃ and
angles in degrees.
The last uncertainty concerns the assignment of the trans
and cis configuration in the diastereoisomers 3a–d. Within
[b]
[b
[b]
rac-1
(R)-1a
(S)-1b
[16]
the framework of a HSAB prebonding analysis, the anti-
Crystal system
Space group
Density
monoclinic
triclinic
P1
1.25
triclinic
P1
1.26
II
symbiotic hypothesis at a Pd metallic center suggests that
P 1 2
1.29
239
1
/n 1
the hardest Pd-coordinating atom (here, the nitrogen atom
of the amine ligand) selects the softest atom in the trans po-
m.p. [8]
220
224
Final R
0.047
0.027
0.0437
sition, namely the naphthyl-PPh group (the benzymidazol-
2
C1-P1
C1-N1
C1-N2
C10-P2
1.808(5)
1.333(6)
1.828(5)
1.434(6)
1.434(6)
75.66
1.8318(11)
1.3188(15)
1.8412(13)
1.4313(14)
1.4313(14)
82.71
1.8296(11)
1.3175(11)
1.8402(12)
1.4277(14)
1.4277(14)
83.05
yl-PPh group is indeed made harder by the two nitrogen
2
[17]
atoms). This hypothesis applies to (R)-cis 3b (Figure 1).
Despite the low selectivity of the complexation process, the
weights of the two cis-isomers should be higher than those
of the two trans-isomers. This supports the tentative assign-
ment proposed at the beginning of the discussion (Figure 3).
N2-C9
[
a]
C10-C9-N2-C1
N2-C9-C10
C9-N2-C1
118.7(4)
128.1(4)
119.01(10)
127.25(9)
119.02(10)
127.15(9)
[
a] Dihedral angle estimated using the Mercury interface. [b] Even con-
sidering the difference in esd values, there is obviously no significant dif-
ferential effects of the packing occurring in the racemate rac-1 and in the
conglomerates (R)-1 and (S)-1.
Evaluation of the (R)-1 and (S)-1 Biminap Ligands in
Tsuji–Trost Asymmetric Catalytic Allylation
The rac-biminap ligand 1 was first tested for its catalytic
properties in the Tsuji–Trost allylation of sodium dimethyl
malonate by 3-acetoxy-1,3-diphenylpropene in presence of a
Using rac-1 in a 2% catalytic ratio and THF as solvent,
the reaction was completed in 20 min. at room temperature
(Table 2, entry 1). Lowering the catalytic ratio to 0.1%, the
II
Pd catalyst (Scheme 3, Table 2).
Chem. Asian J. 2010, 5, 1225 – 1231
ꢂ 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemasianj.org
1227

Y. Canac, R. Chauvin et al.
FULL PAPERS
3
1
Figure 3. Tentative assignement of the P NMR signals for the four dia-
stereoisomeric palladium complexes 3a–d, in accordance with the anti-
symbiotic hypothesis in a prebonding HSAB analysis.
Figure 4. ORTEP view of the X-ray crystal structure of the pre-catalyst
4
a–b with thermal ellipsoids drawn at the 30% probability level (for
clarity, triflate anion and H atoms are omitted). Selected bond distances
ꢃ) and angles (8): C1–P1 1.822(4), C1–N1 1.302(5), C1–N2 1.379(5), P1–
Scheme 3. 1,3-diphenylallylation of sodium dimethyl malonate catalyzed
by Pd-biminap complexes.
(
Pd1 2.2977(9), P2–Pd1 2.3068(9), C10–P2 1.837(4), N2–C9 1.415(5), C10-
C9-N2-C1 72.42.
reaction was almost complete in 72 h (entry 4). Similar activ-
ities were obtained when THF was replaced by CH Cl (en-
The asymmetric version of the catalysis was then investi-
gated by using the pure enantiomer (R)-biminap 1a
(Table 3). In THF with a 2% catalytic ratio, the reaction
proceeded in 44% ee (entry 1). Under the same conditions,
the use of (R)-binap ligand led to the allylated malonate in
2
2
tries 1 and 5). In the same conditions, the rac-binap-Pd cata-
lyst is slightly less efficient than the rac-1 catalyst (entries 1
and 7). These results clearly demonstrate the noticeable effi-
ciency of the rac-biminap-Pd catalyst, in agreement with
previous emphasis that electron-poor ligands are specifically
Table 3. Pd-catalyzed allylation of sodium dimethyl malonate by 3-ace-
toxy-1,3-diphenylpropene in the presence of (R)-biminap or (R)-binap li-
gands (Scheme 3).
[18]
suitable for the Tsuji–Trost allylation reaction. Changing
3
the neutral dimeric Pd precursor [Pd CAHTUNGTRNEUNG( h -C H )Cl] by its cat-
3 5 2
[
c]
[e]
3
[19]
Entry
L
A
T
N
T
N
U
G
Solvent
THF
ee [%]
Yield [%]
ionic monomeric analogue [Pd
ACHTUNGTRENNUN(G h -C H ) AHCTUNGENTRUNG( CH CN) ] AHCTNGTRUENUNG[ OTf]
3 5 3 2
[
[
a]
a]
1
2
3
4
5
(R)-1
(R)-1
(R)-binap
(R)-1
(R)-1
2
2
2
2
2
44 (S)
77 (S)
25 (S)
90 (S)
90 (S)
3
96
95
89
95
95
led to similar results regarding both conversions and isolated
[20]
CH
THF
CH Cl
CH Cl
2
Cl
2
yields (entries 5 and 6). The corresponding pre-catalyst 4
was prepared in 75% yield by reacting rac-biminap 1 with
this cationic precursor (Figure 4). Complex 4 was actually
isolated as a 50:50 mixture of two diastereoisomeric forms
[
a]
[b]
2
2
2
[
b,d]
2
[
a] 2 equiv of ligand )Cl]
[b] 1 equiv of ligand L with respect to [Pd ACHTUGNTRENNUNG( h -C H ) AHCNUTGTREG(UNNN CH CN) OTf] in
mol%. [c] The ee value was determined by H NMR spectroscopy using
the chiral shift reagent (+)-Eu(hfc) ; the absolute configuration (in
brackets) was determined by comparison with literature data (see experi-
L
A
T
N
T
E
N
N
(h -C
3
H
5
2
in mol%.
3
4
a and 4b, likely resulting from a slow 1808-rotary flip of
3 5
3
2
1
the p-allyl ligand and from some restricted rotation about
3
the N-naphthyl or/and PdꢀCN bonds. Yellow single crystals
2
of complex 4 were submitted to X-ray diffraction analysis
[22]
mental section).
(1 equiv) was used instead of NaH/CH2
product determined after purification by chromatography over silica gel.
[d] BSA (1 equiv)/AcOK (cat.)/CH
2 2 2
ACHTUNGTRENNUNG( CO Me)
[15]
which allowed for a structural determination (Figure 4).
ACHTUNGTRENNUNG
(CO Me) . [e] Yield of isolated
2
2
[19]
2
5% ee only (entry 3).
Changing the solvent from
THF to CH Cl resulted in an
Table 2. Pd-catalyzed allylation of sodium dimethyl malonate by 3-acetoxy-1,3-diphenylpropene in the pres-
ence of racemic biminap and binap ligands (Scheme 3).
[c]
[d]
Entry
L
A
H
U
G
E
N
N
[Pd-L] [%]
Solvent
Conversion [%]
Time [mins]
Yield [%]
2
2
[
[
[
[
[
[
a]
a]
a]
a]
a]
b]
increased enantioselectivity of
1
2
3
4
5
6
7
rac-1
rac-1
rac-1
rac-1
rac-1
rac-1
2
1
0.2
0.1
2
THF
THF
THF
THF
100
100
100
94
100
100
100
20
30
720
4320
20
90
92
93
91
95
85
89
77% ee (entries 1 and 2). In ad-
[21]
dition to this solvent effect,
the ee was found to be sensitive
to the nature of the anion.
CH
CH
2
Cl
Cl
2
2
2
2
2
20
30
[
a]
Using the cationic precursor
rac-binap
THF
3
3
[Pd
A
H
U
G
R
N
U
G
3
5
A
H
U
G
R
N
U
G
3
2
ACHTUNGTRENNUNG[ OTf]
[
a] 2 equiv of ligand L with respect to [Pd
H ) ACHTUNGTRENNUNG( CH CN) ] ACHTUNGTRENNUNG[ OTf] in mol%. [c] Conversion determined by H NMR spectroscopy. [d] Yield of isolated
3 5 3 2
product determined after purification by chromatography over silica gel.
A
H
U
G
R
N
N
(h -C
3
H
5
2
)Cl] in mol%. [b] 1 equiv of ligand L with respect to [Pd-
1
3
instead of the neutral dimer
A
C
H
T
U
N
G
T
R
E
N
N
U
N
G
(h -C
3
[Pd ACHTUGNTRNEUN(G h -C H )Cl] , the catalytic
3 5 2
1228
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ꢂ 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Asian J. 2010, 5, 1225 – 1231

Resolution of the Atropochiral Biminap Ligand
A
B
B
B
allylation indeed proceeded in 90% ee (entries 2 and 4).
C ), 150.2 (s, C ), 146.9 (d, JCP =66.6, C ), 143.2 (d, JCP =13.5, C ), 142.8
(
A
d, JCP =11.3, C ), 135.7 (s, C), 135.5 (s, C), 135.0–134.0 (m, CH), 133.7
This effect is consistent with recent results using the binap
[19]
(d, JCP =4.1, C), 132.5–131.9 (m, CH, C), 131.8 (s, CH), 131.7 (s, CH),
31.6 (s, CH), 131.2 (d, JCP =5.0, C), 130.9 (d, JCP =9.3, CH), 130.3–130.1
m, CH), 129.7 (d, JCP =11.3, CH), 129.5 (d, JCP =10.1, CH), 129.2 (d,
CP =10.1, CH), 129.1–128.8 (m, CH, C), 128.4 (s, CH), 128.3–128.1 (m,
CH), 127.8 (s, CH), 126.5 (brs, CH), 126.3 (s, CH), 126.2 (d, JCP =28.9,
C) 125.5 (s, CH), 125.3 (s, CH), 125.1 (s, CH), 124.6 (d, JCP =6.3, CH),
24.5 (s, CH), 124.3 (s, CH), 124.0 (s, CH), 123.4 (s, CH), 122.6 (d, JCP
9.0, C), 120.7 (s, CH), 120.6 (d, JCP =37.7, C), 120.5 (s, CH), 112.6
ligand. However, no effect on the ee value was observed
1
(
J
when BSA/AcOK was used instead of NaH (entry 5).
,
Conclusions
1
4
(
=
The chiral biminap ligand was resolved, and Pd biminap
complexes proved to be efficient for the catalysis of Tsuji–
Trost allylation in terms of both activity and enantioselectiv-
ity. Although the benzimidazolyl-phosphine end provides
the biminap ligand with a moderately electron-poor charac-
ter, the design of new ligands that reduce the s-donation of
A
B
B
A
A+B
CH ), 111.7 (CH ), 74.0 (brs, CH ), 73.7 (brs, CH ), 55.4 (CH
50.7 (s, CH ), 49.5 (s, CH ), 24.6 (CH ), 23.8 ppm (CH
3 3 3 3
CDCl
.42 (d, J=47.4, P
PF ).
c–d. NMR assignment: major isomer tentatively assigned to (S)-cis
3
),
). P NMR
), 26.33 (d, J=47.4, P ),
), ꢀ144.23 ppm (sept, J=712.5,
A
B
A
B
31
(
3
, 202.54 MHz): d=37.65 (d, J=46.3, P
A
B
8
B
), 4.05 (d, J=46.3, P
A
6
A
3
(
B
1
55%), minor isomer (S)-trans (45%). H NMR (CDCl
d=8.54 (m, 1H, Har ), 7.86 (d, JHH =8.7, 1H, Har), 7.79 (d, JHH =8.2, 1H,
3
, 500.33 MHz):
[23]
the phosphine/phosphite ligands remains a challenge for
A
[24]
catalysis. Within this context, the cationic amidiniophos-
phane ligands (also described as NHC-phosphenium ad-
H
H
ar), 7.75–7.65 (m, 19H, Har), 7.56–7.01 (m, 37H, Har), 6.95–6.82 (m, 6H,
ar), 6.77 (brd, JHH =7.0, 1H, Har ), 6.69 (pseudo-q, JHH =JHP =JHP =7.3,
A
B
[10,17,25]
1H, Har ), 6.60 (d, JHH =8.5, 1H, Har), 6.53 (pseudo-q, JHH =JHP =JHP
.8, 1H, Har ), 6.48 (t, JHH =7.6, 2H, Har), 5.96 (d, JHH =8.1, 1H, Har),
.41 (pseudo-quint, JHH =JHP =5.8, 1H, CH ), 4.35 (pseudo-quint, JHH
JHP =5.8, 1H, CH ), 2.47 (brs, 3H, NCH ), 2.39 (d, J =6.7, 3H,
CH
NCH
60.7 (dd, JCP =4.3, JCP =11.1, C ), 159.7 (dd, JCP =3.3, JCP =7.9, C ),
47.8 (d, JCP =2.0, C ), 147.1 (d, JCP =1.0, C ), 146.5 (dd, JCP =2.6, JCP
3.0, C ), 145.6 (dd, JCP =79.5, JCP =5.7, C ), 143.1 (d, JCP =13.8, C ),
42.6 (d, JCP =11.3, C ), 136.3 (s, C), 135.7 (s, C), 135.4–134.4 (m, CH,
=
ducts) have attracted recent interest.
The N-alkylated
A
6
4
version of biminap, termed as bimionap, has been devised as
a highly electron-poor ligand, and both free bimionap and
complexes thereof have been synthesized in the racemic
series. Their enantiomeric pure versions are directly accessi-
ble by alkylation of resolved (R)- or (S)-biminap, and their
study will be shortly reported.
A
=
B
A
3
HH
A
B
B
3
), 2.37 (d, JHH =7.7, 3H, CH
), 2.00 ppm (s, 3H, NCH
3
), 2.19 (brs, 3H, NCH
). C NMR (CDCl
3
), 2.10 (s, 3H,
, 125.82 MHz): d=
A
B
3
13
3
3
A
B
1
1
6
1
A
B
=
B
A
B
A
C), 133.4 (d, JCP =3.8, C
32.0 (s, CH), 131.8 (d, JCP =2.1, CH
JCP =2.6, CH ), 131.4 (s, C), 131.3 (s, C), 131.2 (d, J =2.7, CH ), 131.1–
A
), 133.2 (brs, CH), 132.5 (s, CH), 132.3 (s, CH),
1
A
), 131.7 (d, JCP =2.0, CH), 131.5 (d,
Experimental Section
A
CP
B
1
1
1
30.8 (m, CH, C), 130.5–130.0 (m, CH, C), 129.6 (d, JCP =10.9, CH
29.5 (d, JCP =10.7, CH ), 129.4 (d, JCP =5.3, C ), 129.2 (d, JCP =5.9, C
29.1 (d, JCP =9.8, CH
A
),
),
General remarks. THF and diethyl ether were dried and distilled over
sodium/benzophenone, pentane, dichloromethane, and acetonitrile over
CaH . All other reagents were used as commercially available. All reac-
2
B
B
A
A
), 128.8 (s, CH), 128.77 (s, CH), 128.6–128.2 (m,
CH), 128.1 (s, CH), 127.8 (s, CH), 127.7–127.2 (m, CH, C), 126.6 (d, JCP
.4, CH ), 126.4 (s, CH), 126.3 (s, CH), 126.1–125.8 (m, CH, C), 125.4
pseudo-t, JCP =JCP =7.2, CH ), 125.1 (s, CH), 125.0 (s, CH), 124.9 (s,
CH), 124.8 (d, JCP =32.0, C ), 124.5 (d, JCP =29.9, C ), 124.4 (s, CH),
24.0 (s, CH), 123.9 (s, CH), 123.7 (s, CH), 123.6 (s, CH), 123.5 (s, CH),
123.4 (s, CH), 121.7 (d, JCP =51.0, C ), 121.1 (d, JCP =37.7, C ), 120.7 (s,
CH), 120.6 (s, CH), 119.7 (d, JCP =51.8, C ), 112.8 (s, CH), 111.7 (s, CH),
=
tions were carried out under argon atmosphere, using Schlenk and
vacuum line techniques. Column chromatography was carried out on
silica gel (60 ꢃ, C.C 70–200 mm). The following analytical instruments
5
B
(
A
1
13
31
A
B
were used. H, C, and P NMR: Bruker ARX 250, DPX 300, AV 500.
1
NMR chemical shifts d are in ppm, with positive values to high frequency
1
13
A
A
3 4
relative to the tetramethylsilane reference for H and C and to H PO
3
1
B
for P.
B
7
2
2
P
ꢀ
6.8 (brs, CH
A
), 76.5 (brs, CH
B 3
), 51.4 (d, JCP =2.3, CH ), 51.2 (d, JCP =
Resolution of rac-biminap 1. Rac-biminap 1 (0.51 g, 0.83 mmol) and (+)-
di-m-chlorobis[(R)-dimethyl(1-(1-naphthyl)ethyl)aminato-C ,N]dipalla-
dium(II) 2 (0.28 g, 0.42 mmol) were placed under an atmosphere of
A
A
B
B
.1, CH
4.8 ppm (s, CH
), 21.41 (d, J=41.2, P
144.23 ppm (sept, J=712.5, PF
3
), 49.6 (d, JCP =2.7, CH
3
), 48.9 (s, CH
, 202.54 MHz): d=33.86 (d, J=40.2,
), 8.88 (d, J=41.2, P ), 2.43 (d, J=40.2, P ),
). 3a–d. MS (FAB ): m/z 916 [M ].
Pd: 916.2220; found: 916.2134.
solution of 1,2-bis(diphenylphosphino)ethane (0.07 g,
.17 mmol) in CH Cl (10 mL) was added a solution of diastereoisomers
a–b (0.18 g, 0.17 mmol) in CH Cl (10 mL). After stirring for 3 h at
3 3
), 24.9 (s, CH ),
2
A
31
3
). P NMR (CDCl
3
A
C
H
T
U
N
G
T
R
E
N
N
U
N
G
A
B
B
A
+
argon in a Schlenk tube. After addition of CH Cl (30 mL), the mixture
2
2
+
6
was stirred at room temperature for 3 h. After evaporation under
vacuum, the residue was dissolved in MeOH (30 mL) and added to a so-
lution of ammonium hexafluorophosphate (0.15 g, 0.91 mmol) in H
30 mL). After stirring at room temperature for 1 h and then extraction
with CH Cl (2ꢄ30 mL), the organic layer was dried over MgSO and
+
HRMS (ES ) calcd for C55
46 3 2
H N P
(
R)-1a. To
a
2
O
0
3
2
2
(
2
2
2
2
4
room temperature, the solvent was removed under vacuum and the resi-
due was purified by flash chromatography (pentane/EtOAc: 80:20)
giving the enantiomer (R)-1a (0.08 g, 76%) as a white solid. Recrystalli-
evaporated under vacuum affording a yellow solid residue as a mixture
of four diastereoisomers 3a–d (0.85 g, 96%). A first crystallization of the
crude mixture from CH
isomers 3a–b as a solid residue which was then recrystallized from
CH Cl /Et O at room temperature affording pure 3a–b (0.37 g, 42%) as
2 2 2
Cl /Et O at room temperature gave mainly the
2 2
zation at room temperature from CH Cl /pentane afforded (R)-1a as
2
D
3
white crystals (m.p.: 219–2218C; ½aꢁ =+10.88, c=0.5 in CHCl
3
).
2
2
2
2
D
3
yellow crystals ½aꢁ =+3978, (c=0.6, CHCl
3
). The mother liquor was
Cl at room
(S)-1b. To
0.17 mmol) in CH
3c–d (0.10 g, 0.17 mmol) in CH
a solution of 1,2-bis(diphenylphosphino)ethane (0.04 g,
then evaporated and after recrystallization from pentane/CH
2
2
2
Cl
2
(5 mL) was added a solution of diastereoisomers
Cl (5 mL). After stirring for 3 days at
temperature, the isomers 3c–d (0.35 g, 40%) were obtained in a pure
2
2
2
3
form as yellow crystals ½aꢁ =ꢀ3558, (c=0.5 in CHCl
3
).
room temperature, the solvent was removed under vacuum and the resi-
due was purified by flash chromatograhy (pentane/EtOAc: 80:20) giving
the enantiomer (S)-1b (0.05 g, 81%) as a white solid. Recrystallization at
D
A
3
(
a–b. NMR assignment: major isomer tentatively assigned to (R)-cis
B
1
3
80%), minor isomer (R)-trans (20%). H NMR (CDCl , 500.33 MHz):
A+B
A+B
2 2
room temperature from CH Cl /pentane afforded (S)-1b as white crystals
d=7.81–7.76 (m, 2H, Har
), 7.71–7.28 (m, 24H, Har
), 7.19–6.77 (m,
2
D
3
A+B
A+B
A+B
(m.p.: 223–2258C; ½aꢁ =ꢀ10.68, c=0.5 in CHCl ).
1
3
1
2H, Har
), 6.64–6.41 (m, 2H, Har
), 4.49–4.45 (m, 1.1H, CH
),
),
3
A+B
A
B
3
3
.53 (s, 3.3H, NCH
3
), 2.08 (s, 3H, NCH
3
), 2.00 (s, 0.3H, NCH
4a–b. A mixture of bis(acetonitrile)-h -allylpalladium triflate (0.13 g,
0.33 mmol) and rac-biminap (0.20 g, 0.33 mmol) was dissolved in
CH Cl (10 mL) and stirred at room temperature for 2 h. After evapora-
A
B
13
.45 (d, J=6.0, 3H, CH
3
), 1.33 ppm (d, J=6.0, 0.3 CH
3
). C NMR
1
A
(
CDCl
3
, 125.82 MHz): d=156.1 (dd, JCP =8.3, JCP =117.9, C ), 150.3 (s,
2
2
Chem. Asian J. 2010, 5, 1225 – 1231
ꢂ 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemasianj.org
1229

Y. Canac, R. Chauvin et al.
FULL PAPERS
tion of the solvent under vacuum, the residue was washed with Et
2
O
SIR92 and refined by full-matrix least-squares procedures on F using the
programs of the PC version of CRYSTALS. Atomic scattering factors
were taken from the International Tables for X-ray Crystallography. All
non-hydrogen atoms were refined anisotropically. Hydrogen atoms were
refined using a riding model. Absorption corrections were introduced
using the program MULTISCAN.
(
20 mL) affording a yellow solid. Recrystallization at room temperature
3
from CH CN gave pale yellow crystals as a mixture (50:50) of two diaste-
reoisomers 4a–b (0.22 g, 75%).
1
H NMR (DMSO, 500.33 MHz): d=7.92–7.82 (m, 4H, Har), 7.76–7.49 (m,
3
4
0H, Har), 7.37–7.28 (m, 6H, Har), 7.15–6.95 (m, 12H, Har), 6.84–6.77 (m,
H, Har), 6.50–6.41 (m, 4H, Harom), 6.26–6.11 (m, 2H, CHAll), 4.31–4.16
For 1b and 4a–b. Data were collected at low temperature on a Bruker
Kappa Apex II diffractometer using graphite-monochromated MoKa radi-
ation (l=0.71073 ꢃ) and equipped with an Oxford Cryosystems Cryo-
stream Cooler Device. The final unit cell parameters have been obtained
by means of a least-squares refinement performed on a set of 9836 well
measured reflections. The structures have been solved by Direct Methods
(
m, 4H, CH2All), 4.02 (pseudo-t,
JHH =JHP =5.2, 1H, CH2All), 3.85
(
pseudo-t, JHH =JHP =5.4, 1H, CH2All), 3.35–3.25 ppm (m, 2H, CH2All).
C NMR (DMSO, 125.82 MHz): d=146.8 (d, JCP =71.6, C), 146.6 (d,
CP =69.7, C), 142.3 (d, JCP =14.8, C), 142.2 (d, JCP =12.6, C), 137.1 (s, C),
1
3
J
1
36.9 (s, C), 135.6 (d, JCP =16.2, CH), 135.5 (d, JCP =15.7, CH), 135.1 (s,
C), 135.0 (s, C), 134.7 (d, JCP =16.7, CH), 134.6 (d, JCP =16.4, CH), 134.5
d, JCP =7.5, C), 134.2 (s, C), 134.1 (d, JCP =14.2, CH), 133.8 (d, JCP =13.8,
CH), 133.5 (d, JCP =13.1, CH), 132.3 (s, CH), 132.0 (s, CH), 131.9 (s,
CH), 131.8 (s, CH), 131.7 (s, CH), 130.9 (d, JCP =45.5, C), 130.6 (d, JCP
.7, CH), 130.4 (d, JCP =30.5, CH), 130.3–129.7 (m, CH, C), 129.3 (d,
CP =15.3, CH), 129.2 (d, JCP =11.4, CH), 129.1 (d, JCP =11.3, CH), 129.0–
2
using SIR92 and refined by means of least-squares procedures on a F
(
with the aid of the program SHELXL97 included in the software package
WinGX version 1.63. The Atomic Scattering Factors were taken from In-
ternational Tables for X-Ray Crystallography. All hydrogens atoms were
located geometrically and refined by using a riding model. All non-hy-
drogen atoms were anisotropically refined, and in the last cycles of re-
finement a weighting scheme was used, where weights were calculated
=
7
J
1
1
1
28.8 (m, CH), 128.6 (s, CH), 128.5 (s, CH), 127.1 (d, JCP =6.1, CH),
25.7 (d, JCP =48.6, C), 125.2 (brs, CH), 124.6 (s, CH), 124.5 (s, CH),
2
2
2
from the following formula: w=1/[s AHCUTNGRNENUG( Fo )+(aP) +bP] where P=
2
2
24.1 (s, CH), 123.8 (s, CH), 123.7 (s, CH), 123.0 (d, JCP =49.9, C), 120.7
(Fo +2Fc )/3.
ꢀ
(
q, JCF =320.8, CF
3
SO
3
), 120.0 (s, CH), 119.9 (s, CH), 113.1 (s, CH),
ꢀ1
1
a. C41H
30
N
2
P
2
, M=612.6 gmol , Triclinic, a=8.9639(7), b=9.3652(8),
1
13.0 (s, CH), 81.7 (d, JCP =27.1, CH2All), 80.4 (d, JCP =27.0, CH2All), 76.1
c=10.9091(9) ꢃ, a=96.684(3), b=95.668(3), g=115.291(3)8, V=
3
1
(
d, JCP =28.6, CH2All), 74.6 ppm (d, JCP =26.9, CH2All). P NMR (DMSO,
02.54 MHz): d=19.69 (d, J=45.8, P ), 19.14 (d, J=45.3, P ), 11.48 (d,
J=45.8, P ), 10.70 ppm (d, J=45.3, P
3
8
11.08(12) ꢃ , T=180 K, space group P 1, Z=1.
2
A
B
ꢀ1
1
b. C41H
30
N
2
P
2
, M=612.6 gmol , Triclinic, a=8.9539(2), b=9.3626(2),
+
+
A
B
). MS (ES ): m/z 759 [M ].
Pd: 759.1326; found: 759.1356.
c=10.9109(4) ꢃ, a=96.682(2), b=95.659(2), g=115.2960(10)8, V=
+
HRMS (ES ) calcd for C44
H
35
N
2
P
2
3
8
10.07(4) ꢃ , T=180 K, space group P 1, Z=1.
Pd, F P, 2(CH Cl ), M=1232.16 gmol , Orthorhombic,
ꢀ
1
3
b. C55
H
46
N
3
P
2
6
A
T
N
T
E
N
N
2
2
Catalytic Allylic Substitution of 3-Acetoxy-1,3-diphenylpropene by
Dimethyl Malonate
3
a=13.3512(3), b=18.3986(4), c=21.9988(5) ꢃ, V=5403.9(2) ꢃ , T=
1
80 K, space group P 2
1
2
1
2
1
, Z=4.
a) Biminap
0.20 g, 0.8 mmol), and [Pd
solved in THF (2 mL). After stirring for 20 min, the mixture was added
at room temperature to suspension of sodium hydride (0.064 g,
.6 mmol) and dimethyl malonate (0.184 mL, 1.6 mmol) in THF (3 mL).
Then the reaction was monitored by TLC following the disappearance of
-acetoxy-1,3-diphenylpropene. After completion, the reaction was
quenched with a saturated aqueous solution of NH Cl (20 mL) and then
extracted with CH Cl (2ꢄ20 mL). The combined organic layers were
dried over MgSO , filtered, and evaporated affording the crude product
which was purified by chromatography on silica gel (EtOAc/pentane:
5:85).
b) Biminap
1
(0.0098 g, 0.016 mmol), 3-acetoxy-1,3-diphenylpropene
ꢀ1
4
1
9
a–b. C44 Pd, CF
H
35
N
2
P
2
3
O
3
S, C H N, M =950.2 gmol , Monoclinic, a=
2 3
(
A
H
U
G
R
N
U
G
2
1.0312(8), b=29.965(2), c=13.1533(10) ꢃ, a=90, b=103.591(3), g=
08, V=4226.0(5) ꢃ , T=180 K, space group P 1 21 1, Z=4.
3
a
1
3
4
Acknowledgements
2
2
4
While thanks are extended to the Ministꢅre de l’Enseignement Supꢁrieur
de la Recherche et de la Technologie and the Universitꢁ Paul Sabatier,
the authors would like to acknowledge the Centre National de la Recher-
che Scientifique for the post-doctoral fellowship of N.D., and the ANR
program (ANR-08-JCJC-0137-01) for financial support. They are also in-
debted to Christine Lepetit for stimulating discussions and to Carine Du-
hayon for X-ray crystal structure determinations.
1
1
(0.0098 g, 0.016 mmol), 3-acetoxy-1,3-diphenylpropene
3
(
0.20 g, 0.8 mmol), and bis-(acetonitrile)-h -allylpalladium triflate
0.006 g, 0.016 mmol) were dissolved in CH Cl (3 mL). After stirring for
0 min, the mixture was added at room temperature to a suspension of
sodium hydride (0.064 g, 1.6 mmol) and dimethyl malonate (0.184 mL,
.6 mmol) in CH Cl (3 mL). Then the reaction was monitored by TLC
(
2
2
2
1
2
2
following the disappearance of 3-acetoxy-1,3-diphenylpropene. After
completion, the reaction was quenched with a saturated aqueous solution
[
1] a) S. Dꢆez-Gonzꢇlez, N. Marion, S. P. Nolan, Chem. Rev. 2009, 109,
612; b) F. E. Hahn, M. C. Jahnke, Angew. Chem. 2008, 120, 3166;
3
of NH
4
Cl (20 mL) and then extracted with CH
2 2
Cl (2ꢄ20 mL). The com-
Angew. Chem. Int. Ed. 2008, 47, 3122; c) S. Wꢈrtz, F. Glorius, Acc.
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bined organic layers were dried over MgSO
giving the crude product which was purified by chromatography on silica
4
, filtered, and evaporated
gel (EtOAc/pentane: 15:85). In both cases, the enantiomeric excess was
1
determined by H NMR spectroscopy using (+)-Eu
A
H
U
G
R
N
N
(hfc)
3
as the chiral
shift reagent. For entry 1 of Table 3, for example, the ee was determined
by integration of the signals of the diastereotopic CO CH nuclei: for the
=+4.22, +4.33 ppm; for the minor isomer
=+4.20, +4.47 ppm. The optical rotation was measured to be
2
3
1
major isomer (72%): d
H
1
[2] a) C. Rosini, L. Eranzini, A. Raffaelli, P. Salvadori, Synthesis 1992,
503; b) R. Noyori, Asymmetric Catalysis in Organic Synthesis, Wiley,
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b) T. T. L. Au-Yeung, A. S. C. Chan, Coord. Chem. Rev. 2004, 248,
2151.
(
28%): d
H
2
5
levorotatory: ½aꢁ =ꢀ10.08 (CHCl
3
, c=1.57). The chemical shifts of the
D
CO
2
CH
3
nuclei of the major isomer, were thus assigned to the (ꢀ)-(S)-
[22]
enantiomer by comparison with the literature data.
[
Crystal Structure Determination of 1a, 1b, 3b, and 4a–b.
For 1a and 3b. Data were collected at low temperature on a Bruker
Kappa Apex II diffractometer using a graphite-monochromated MoKa ra-
diation (l=0.71073 ꢃ) and equipped with an Oxford Cryosystems Cryo-
stream Cooler Device. Structures were solved by direct methods using
[4] a) T. Benincori, E. Brenna, F. Sannicolꢉ, L. Trimarco, P. Antognaz-
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1230
www.chemasianj.org
ꢂ 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Asian J. 2010, 5, 1225 – 1231

Resolution of the Atropochiral Biminap Ligand
Sannicolꢉ, T. Pilati, Phosphorus Sulfur and Silicon 1999, 144–146,
data for this paper. These data can be obtained free of charge from
The Cambridge Crystallographic Data Centre at www.ccdc.cam.a-
c.uk/data_request/cif.
4
05.
[
[
5] a) A. Miyashita, A. Yasuda, H. Takaya, K. Toriumi, T. Ito, T.
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48, 5562.
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Org. Lett. 1999, 1, 953.
[18] N. T. Barczak, R. E. Grote, E. R. Jarvo, Organometallics 2007, 26,
4863.
[19] L. A. Evans, N. Fey, J. N. Harvey, D. Hose, G. C. Lloyd-Jones, P.
Murray, A. G. Orpen, R. Osborne, G. J. J. Owen-Smith, M. Purdie, J.
[
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[
Am. Chem. Soc. 2008, 130, 14471.
3
1
15, 7033.
[20] Cationic complex [Pd
A
H
U
G
R
N
U
G
3
H
5
)
A
H
U
G
R
N
U
G
3
CN)
2
OTf] could not be tested in
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15] CCDC 755393
CCDC 755392
A
C
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T
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N
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(1a), CCDC 755394
A
H
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N
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G
A
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G
Received: November 21, 2009
Published online: March 25, 2010
A
C
H
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T
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E
N
N
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(4a--b) contain the supplementary crystallographic
Chem. Asian J. 2010, 5, 1225 – 1231
ꢂ 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemasianj.org
1231