Palladacycle mediated synthesis of cyano-functionalized chiral 1,2-diphosphine and subsequent functional group transformations

Article abstract of DOI:10.1016/j.jorganchem.2010.10.029

Cyano-functionalized allylic phosphine substrates containing the ortho-metalated (R)-(1-(dimethylamino)ethyl)naphthalene as the chiral auxiliary were synthesized from bromoacetaldehyde dimethylacetal via a one-pot process. The diastereoselective hydrophos

Full text of DOI:10.1016/j.jorganchem.2010.10.029

Journal of Organometallic Chemistry 696 (2011) 905e912
Contents lists available at ScienceDirect
Journal of Organometallic Chemistry
journal homepage: www.elsevier.com/locate/jorganchem
Palladacycle mediated synthesis of cyano-functionalized chiral 1,2-diphosphine
and subsequent functional group transformations
*
Mingjun Yuan, Sumod A. Pullarkat, Yongxin Li, Pak-Hing Leung
Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University, Singapore 637371, Singapore
a r t i c l e i n f o
a b s t r a c t
Article history:
Cyano-functionalized allylic phosphine substrates containing the ortho-metalated (R)-(1-(dimethylamino)
ethyl)naphthalene as the chiral auxiliary were synthesized from bromoacetaldehyde dimethylacetal via
a one-pot process. The diastereoselective hydrophosphination reactions of the cis- and trans-allylic
phosphine substrates gave the cyano-functionalized chiral 1,2-bis(diphenylphosphino)ethane products
with high yield and stereoselectivity. The subsequent organic transformation reactions of the cyano-
substituted products chemoselectively afforded the formyl- and hydroxyl-functionalized chiral 1,2-
diphosphine complexes with retention of stereochemistry. The coordination properties and absolute
configurations of the novel 1,2-diphosphine complexes were established by single crystal X-ray crystal-
lography. The optically pure 1,2-bis(diphenylphosphino)ethane ligands with cyano-, formyl- and hydroxyl-
functionalities could be liberated in high yields from the corresponding dihalo palladium complexes by
treatment with aqueous potassium cyanide.
Received 7 August 2010
Received in revised form
5 October 2010
Accepted 12 October 2010
Available online 23 October 2010
Keywords:
Allylic phosphine
Asymmetric hydrophosphination
Chiral diphosphine
Palladacycle
Ó 2010 Elsevier B.V. All rights reserved.
1. Introduction
past few years, our group has revealed that the organopalladium
complexes containing (R)- or (S)-(1-(dimethylamino)ethyl)naphtha-
Optically pure chiral diphosphines containing the 1,2-bis(diphe-
nylphosphino)ethane backbone, such as (S,S)-chiraphos [1e9] and
(S)-prophos [10e15], are a class of powerful auxiliaries in transition
metal catalyzed asymmetric reactions. For example, Carmona et al.
reported the enantioselective 1,3-dipolar cycloaddition of C,N-
diphenylnitrone to methacrolein catalyzed by rhodium/(S)-Prophos
complex with up to 90% ee [15]. It has been well established that the
presence of proper functionalities, for instance hydroxyl, amino, or
ester group on these chiral phosphine frameworks can efficiently
improve both the reactivity and enantioselectivity in many reactions
through the secondary interactions with the reacting substrates
[16e21]. However, optically pure functionalized diphosphines are
more difficult to synthesize partly due to the lack of a natural pools
when compared to their non-functionalized analogues. On the other
hand, the reactive functional groups in the reaction substrates usually
make the synthesis tedious due to the protection and deprotection
required during organic manipulations [22e27].
lene as the chiral auxiliary are good promoters for asymmetric
hydrophosphination reactions [35e43]. In the courseof theseseries of
studies, the substituted vinylic phosphine species have been exten-
sively employed as reaction precursors to synthesize the chiral
versions of these functionalized diphosphine ligands [35e39].
Quite recently, we have also reported the synthesis of ester- and
keto-substituted allylic phosphine substrates and found that they are
good reaction precursors towards Michael-type hydrophosphination
to synthesize ester- and keto-functionalized chiral 1,2-bis(diphenyl-
phosphino)ethanes with high regio- and stereoselectivities [41].
Continuing our interests in the development of such new chiral
diphosphine ligands with designed functionalities and further
application of the chiral organopalladium complex in asymmetric
transformations, herein, we report a facile synthesis of cyano-func-
tionalized allylic phopshine substrates. As the cyano group has been
shown to be easily derivatized with versatility and selectivity
[44e53], the subsequent hydrophosphination and functional group
transformation reactions generate the cyano-, formyl-, and hydroxyl-
functionalized 1,2-bis(diphenylphosphino)ethane ligands with high
stereoselectivities.
The addition of secondary phosphines to carbonecarbon double
bonds, known as hydrophosphination, is the most valuable and
convenient process for synthesis of functionalized tertiary phosphine
ligands [28e34]. In principle, when the phosphorus atom is incor-
porated into olefin precursors, the subsequent hydrophosphination
reactionscanproduceaclassofusefuldiphosphineligands.Duringthe
2. Results and discussion
Scheme 1 shows the one-pot synthesis of cyano-functionalized
monophosphine palladium complex R-3. The bromoacetaldehyde
* Corresponding author. Tel.: þ65 63168905; fax: þ65 63166984.
E-mail address: pakhing@ntu.edu.sg (P.-H. Leung).
0022-328X/$ e see front matter Ó 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2010.10.029

906
M. Yuan et al. / Journal of Organometallic Chemistry 696 (2011) 905e912
dimethylacetal reacted smoothly with sodium diphenylphosphide,
and upon hydrolysis with 4 N HCl acid, the resultant intermediate
was in situ treated with (triphenylphosphoranylidene)acetonitrile
to afford the allylic phosphine species 4-(diphenylphosphino)but-2-
enenitrile 1. The free phosphine ligand was not isolated and was
subsequently coordinated to the palladium complex R-2 to generate
the monomeric allylic phosphine complex R-3 as a mixture of the
cis/trans (1:1.6) isomers in 85% yield. It is noteworthy that the low
cis/trans selectivity provides an opportunity to isolate and charac-
terize the two isomeric template complexes for the subsequent
hydrophosphination reactions. The trans-isomer, trans-R-3, could be
easily separated by fractional crystallization from ethyl acetate and
hexanes as yellowish square crystals, with [
a
]
¼ ꢀ55.4ꢁ (c 0.8,
D
CH2Cl2). The 202 MHz 31P NMR spectrum in CDCl3 of the trans-R-3
exhibited a sharp singlet at
d 33.7. The remaining cis-isomer in
mother liquor was concentrated and recrystallized from benzene
and n-pentane to afford cis-R-3 as yellowish needles in 32.6% overall
yield with [
signal at
a
]D ¼ þ146.7ꢁ (c 0.9, CH2Cl2), and a single resonance
Fig. 1. Molecular structure of complex trans-R-3.
d
32.5 was observed in the 31P NMR spectrum.
The molecular structure and coordination property of trans-R-3
were studied by means of X-ray crystallography. The ORTEP drawing
of molecule is shown in Fig. 1, while the selected bond length, angle,
and other crystallographic parameters are listed in Table 1 and Table
4. As expected, the monodentate phosphorus donor atom is located
Hence the hydrophosphination process proceeded with high
stereospecificity, as complexes 5a and 6a are a pairofregioisomers on
the metal which adopted the same S absolute configuration at the
newly generated stereogenic carbon centers.
regioselectively trans to the s-donating nitrogen group of the chiral
The chiral naphthylamine auxiliary on products 5a and 6a could
be chemoselectively removed by treatment of the isomers with
concentrated hydrochloric acid in the presence of NaI (Scheme 3)
[54]. Thus, the optically pure diiodo palladium complex 9a was
auxiliary. The Pd atom adopts the distorted square planar coordina-
tion geometry, with the angles around the metal center in the ranges
of81.0(1)e96.7(1) and170.2(1)e170.5(1)ꢁ. The C16eC17 bondlength
ꢀ
is 1.334(2) A which clearly exhibits the double bond character.
obtained as red cubic crystals in 94% yield, [
a
]D ¼ þ58.2ꢁ (c 0.6,
CH2Cl2). The 31P NMR spectrum (CD2Cl2, 202 MHz) of product 9a
exhibited a pair of doublets at
d
43.7, 61.7 (JPP ¼ 12.0 Hz). The
2.1. Asymmetric hydrophosphination of cyano-functionalized allylic
phosphine palladium complex R-3
molecular structure and the absolute stereochemistry of diiodo
complex 9awere studied by X-raycrystallographic analysis. There are
two crystallographically distinguishable molecules in the asym-
metric unit with similar bond lengths and the same S absolute
configuration at the newly formed chiral center. Fig. 2 shows the
structure ofmolecule 2; and the selected bondand angles are givenin
Table 2. The coordination geometry around Pd atom is the expected
distorted square planar. The PdP2 plane is rotated at an angle of 9.3
(1)ꢁ with respect to that of PdI2, and the angles around the palladium
center are in the ranges of 86.2(1)e92.6(1) and 170.7(1)e175.5(1)ꢁ.
The PdeP bonds (2.257(2) and 2.279(2) A) are apparently larger than
in the case of similar dichloro 1,2-diphosphine metallacycles
[35e43]. The five-membered diphosphine chelate adopts the
conformationwiththecyano group occupyingthe stericallyfavorable
equatorial position.
Initially, the Z-form isomer, cis-R-3, is employed for the asym-
metric addition reaction and the synthetic methodology adopted is
shown in Scheme 2. The chloro ligand in cis-R-3 is well known to be
both kinetically and thermodynamically stable, and is inert to
displacement by incoming phosphorus donor atoms [35e39].
Treatment of the chloro complex with aqueous silver perchlorate
yielded the cationic perchlorato intermediate cis-R-4 in essentially
quantitative yield. This highly reactive species was not isolated and
was subsequently reacted with a stoichiometric amount of diphe-
nylphosphine at ꢀ78 ꢁC to yield the desired hydrophosphination
products. The reaction was monitored by 31P NMR spectroscopy and
was found to be complete within 2 h. Prior to purification, the
202 MHz 31P NMR spectrum of the crude product in CDCl3 exhibited
ꢀ
d ring
As indicated in Scheme 3, treatment of diiodo complex 9a with
aqueous potassium cyanide conveniently gave the optically pure
two pairs of doublets at
(JPP ¼ 33.8 Hz), which indicated the formation of products 5a and 6a.
d
28.7, 62.4 (JPP ¼ 33.5 Hz), and 43.5, 49.1
1. HCl
2. Na2CO3
Ph
O
Ph2P-Na
Ph
P
O
P
Br
O
O
Ph
Ph
O
N
Cl
N
Pd
Cl
P
Pd
CN
Ph
P
2
Ph3P
2
R-
CN
CN
Ph
Ph
Ph
3
1
R-
Scheme 1.

M. Yuan et al. / Journal of Organometallic Chemistry 696 (2011) 905e912
907
Table 1
Selected bond lengths (A) and angles ( ) of trans-R-3.
(JPP ¼ 24.5 Hz), with the intensity ratio of 26.5:4.5:2.0:1.0, respec-
tively. The 31P NMR signals indicated that, besides the two major
regioisomers 5a and 6a, a new pair of regioisomers 7a and 8a with
doublets at 44.0, 48.3 (JPP ¼ 31.3 Hz) and 37.3, 73.7 (JPP ¼ 24.5 Hz),
which adopted the same R absolute configuration at the chiral carbon
center, were also formed as the minor products during the addition
reaction. Apparently, the absolute stereoselectivity at the newly
formed chiral carbon center in the case of hydrophosphination of
trans-R-3 is 10.3: 1. The two major regioisomers 5a and 6a could be
isolated by a slow column chromatography on silica, or by slow
diffusion of diethyl ether into the acetonitrile solution as an off-white
solid.
ꢁ
ꢀ
Pd1eC1
Pd1eCl1
P1eC15
C16eC17
Cl1ePd1eN1
P1ePd1eC1
N1ePd1eP1
P1eC15eC16
2.001(1)
2.384(1)
1.848(1)
1.334(2)
93.4(1)
96.7(1)
170.5(1)
109.4(1)
Pd1eN1
Pd1eP1
C15eC16
C17eC18
Cl1ePd1eP1
N1ePd1eC1
C1ePd1eCl1
C15eC16eC17
2.142(1)
2.250(1)
1.489(2)
1.434(2)
90.1(1)
81.0(1)
170.2(1)
122.8(1)
cyano-functionalized 1,2-diphosphine ligand 10a as a white solid in
high yield, [
a
]D ¼ ꢀ113.6 (c 1.3, CH2Cl2). The 202 MHz 31P NMR
2.2. Functional group transformations: synthesis of formyl- and
hydroxyl-functionalized 1,2-diphosphine products
spectrum in CDCl3 of the free chiral ligand showed a pair of
doublets at
d
ꢀ6.0, ꢀ22.8 (JPP ¼ 24.1 Hz). As illustrated in Scheme 4,
in order to confirm the optical purity of the free phosphine ligand
10a, the liberated ligand was recoordinated to the bis(acetonitrile)
complex R-11. The 31P NMR spectrum of the resultant recomplex-
ation products in CDCl3 expectedly exhibited two pair of doublets at
It has been well established that the cyano group could be easily
converted to other functionalities such as acid, amide, amine, alde-
hyde, or alcohol by simple organic manipulations [44e53]. However,
the organic transformations involving chiral diphosphine ligand on
Pd(II) complex with chiral amine auxiliaryare not common due to its
inherent kinetic and chemical instability. For example, the reductive
decomplexation occurs when the diphosphine palladium complexes
containing (R)-(1-(dimethylamino)ethyl)-benzene as the chiral
auxiliary were treated with LiAlH4 [55,56]. However, as illustrated in
Scheme 3, the regioisomers 5a and 6a could be chemoselectively
converted into the formyl-functionalized complexes 5b and 6b by
reduction with DIBAL-H at ꢀ78 ꢁC for 6 h. The 202 MHz 31P NMR
spectrum in CDCl3 of the reduction products showed two new pairs
d
28.7, 62.4 (JPP ¼ 33.5 Hz), and 43.5, 49.1 (JPP ¼ 33.8 Hz), which
were apparently due to the formation of the original regioisomeric
products 5a and 6a. As a further check, two new regioisomers 12a
and 13a were prepared by recoordination of the chiral diphosphine
ligand 10a with the equally accessible enantiomeric complex S-11.
The 31P NMR spectrum of complexes 12a and 13a exhibited two
distinct pairs of doublet phosphorus signals at
(JPP ¼ 24.5 Hz), and 44.0, 48.3 (JPP ¼ 31.3 Hz). Importantly, no
phosphorus NMR peaks were observed at 28.7, 43.5, 49.1, and
62.4, and the cyano-functionalized chiral 1,2-diphosphine 10a was
thus confirmed to be optically pure.
For comparison of the stereoselectivity, the E-form isomeric
substrate trans-R-3 was also employed for the asymmetric hydro-
phosphination reaction. However, upon treatment of the perchlorate
intermediate trans-R-4 with diphenylphosphine under similar reac-
tion conditions, the 31P NMR spectrum of the crude products
d 37.3, 73.7
d
of doublet signals at
d
30.9, 65.5 (JPP ¼ 32.3 Hz) and 45.7, 51.3
(JPP ¼ 33.6 Hz). Similarly, the regioisomers 5b and 6b were treated
with concentrated hydrochloric acid to remove the chiral naph-
thylamine auxiliary. The neutral dichloro complex 9b with a pair of
doublets at
solid in 87% yield, [
to crystallize the formyl-functionalized dichloro complex 9b from
various solvent systems to get suitable crystals for X-ray crystallo-
graphic study were unsuccessful.
d
52.9, 71.4 (JPP ¼ 6.5 Hz) was thus isolated as a white
a
]D ¼ þ52.5ꢁ (c 0.8, CH2Cl2). Unfortunately, efforts
exhibited four pairs of doublets at
62.4 (JPP ¼ 33.5 Hz); 44.0, 48.3 (JPP ¼ 31.3 Hz); and 37.3, 73.7
d
43.5, 49.1 (JPP ¼ 33.8 Hz); 28.7,
Further treatment of 9b with aqueous potassium cyanide
liberated the chiral diphosphine ligand 10b as a white solid in 92%
¼ ꢀ102.7ꢁ (c 1.1, CH2Cl2). The liberated free ligand indi-
N
N
yield, [a]
cated a pair of doublets at
spectrum. The subsequent recoordination process confirmed the
optical purity of the formyl-functionalized 1,2-diphosphine ligand
10b (Scheme 4). The 31P NMR spectrum of the recomplexation of
10b with the bis(acetonitrile) complex R-11 showed two pairs of
D
OClO3
P
Cl
P
ꢀ1.4, ꢀ22.0 (JPP ¼ 27.4 Hz) in 31P NMR
AgClO4
Ph2PH
d
Pd
Pd
CN
CN
Ph
4
Ph
Ph
Ph
3
R-
R-
doublets at
d
30.9, 65.5 (JPP ¼ 32.3 Hz) and 45.7, 51.3 (JPP ¼ 33.6 Hz),
which indicated the generation of the original regioisomers 5b and
6b. On the other hand, the recomplexation products involving S-11
gave two new regioisomers 12b and 13b with two pairs of different
Ph Ph
P
PhPh
P
H
N
N
CN
doublets at
d
38.3, 74.4 (JPP ¼ 24.3 Hz) and 46.2, 50.1 (JPP ¼ 30.6 Hz).
Pd
Pd
CN
As shown in Scheme 3, further reduction of formyl-functional-
ized regioisomers 5b and 6b by treatment with DIBAL-H could
chemoselectively yield the hydroxyl-functionalized products 5c
and 6c. The new regioisomers exhibited two pairs of doublets at
P
Ph Ph
P
PhPh
H
ClO4
6a
ClO4
5a
d
31.2, 66.2 (JPP ¼ 33.4 Hz) and 47.3, 52.4 (JPP ¼ 33.5 Hz) in 202 MHz
31P NMR spectrum. Upon removal of the chiral naphthylamine
auxiliary of complexes 5c and 6c with concentrated hydrochloric
acid, the optically pure dichloro complex 9c was crystallized as
colorless square crystals from dichloromethane and diethyl ether in
PhPh
P
PhPh
P
H
N
N
CN
Pd
Pd
CN
P
P
PhPh
¼ þ51.9 (c 0.5, CH2Cl2). The 31P NMR spectrum
H
86% yield, [a]
(202 MHz, CD2Cl2) showed a pair of doublets at
D
PhPh
d 51.6, 72.0
ClO4
8a
ClO4
7a
(JPP ¼ 5.8 Hz). The single-crystal X-ray diffraction analysis clearly
established its coordination mode and the absolute configuration
(Fig. 3). The geometry around the palladium center is square planar
Scheme 2.

908
M. Yuan et al. / Journal of Organometallic Chemistry 696 (2011) 905e912
PhPh
PhPh
Ph Ph
P
PhPh
P
H
N
HCl
NaI
N
H
H
P
P
I
KCN
CN
CN
CN
Pd
Pd
Pd
CN
P
I
P
Ph Ph
P
PhPh
P
PhPh
H
PhPh
ClO4
5a
ClO4
6a
9a
10a
DIBAL-H
PhPh
P
Ph Ph
P
PhPh
P
PhPh
P
H
N
N
H
H
KCN
KCN
CHO
HCl
HCl
Cl
Cl
CHO
CHO
Pd
Pd
Pd
CHO
P
P
Ph Ph
P
PhPh
P
PhPh
H
PhPh
ClO4
6b
ClO4
5b
10b
9b
DIBAL-H
PhPh
P
Ph Ph
P
PhPh
P
PhPh
P
H
N
N
H
H
OH
OH
OH
Cl
Cl
Pd
Pd
Pd
P
P
OH
P
P
PhPh
H
PhPh
Ph Ph
PhPh
ClO4
6c
ClO4
5c
9c
10c
Scheme 3.
with slight tetrahedral distortion (2.1ꢁ). Both bond lengths and
angles are comparable with the similar diphosphine chelating rings
previously reported [35e43] as populated in Table 3. Apparently,
the S absolute configuration at the chiral carbon center remained
unchanged during the functional group transformation process.
The subsequent liberation of chiral hydroxyl-functionalized 1,2-
diphosphine ligand 10c [27] was achieved by treatment of the
dichloro palladium complex with aqueous potassium cyanide
(Scheme 3). Thus the enantiomerically active free diphosphine
ligand was obtained as a white solid in 96% yield, with a pair of
doublets at
d
ꢀ1.0, ꢀ19.8 (JPP ¼ 21.2 Hz) in the 202 MHz 31P NMR
spectrum. The optical purity of 10c was confirmed by a similar
recomplexation process (Scheme 4). It is important to note that the
recoordination products involving the bis(acetonitrile) complex S-11
revealed two pairs of doublets at
d
39.6, 76.9 (d, JPP ¼ 23.6 Hz) and
47.8, 50.2 (d, JPP ¼ 32.2 Hz) in the 31P NMR spectrum, which indicated
the formation of the new regioisomers 12c and 13c. The recoordi-
nation reaction therefore confirmed that the chiral hydroxyl-
substituted 1,2-diphosphine 10c was enantiomerically pure.
In summary, we have presented an efficient synthesis of chiral1,2-
diphosphine ligand with cyano-functionality via organopalladium
complex promoted hydrophosphination of functionalized allylic
monophosphine substrates. The addition reaction proceeded with
high yield and stereoselectivity under mild conditions. The subse-
quent functional group transformation reactions of the hydro-
phosphination products chemoselectively produced the formyl- and
hydroxyl-substituted chiral diphosphine ligands with retention of
stereochemistry. Investigations on other organic transformations of
the cyano group to synthesize new chiral 1,2-diphosphine ligands,
and the screening of catalytic reactions by employing these optically
active diphosphines are currently in progress.
3. Experimental
Reactions involving air-sensitive compounds were performed
under a positive pressure of argon using standard Schlenk line.
Solvents were dried according to standard procedures and degassed
Table 2
ꢁ
ꢀ
Selected bond lengths (A) and angles ( ) of 9a.
Pd2eP3
Pd2eP4
C43eP3
C44eP4
I3ePd2eI4
P4ePd2eI4
P4ePd2eI3
2.279(2)
2.257(2)
1.891(9)
1.863(8)
92.6(1)
Pd2eI3
Pd2eI4
C43eC44
P3ePd2eP4
P3ePd2eI3
P3ePd2eI4
P3eC43eC44
2.640(1)
2.643(1)
1.565(11)
86.2(1)
90.3(1)
175.5(1)
107.4(6)
91.5(1)
170.7(1)
Fig. 2. Molecular structure and absolute stereochemistry of complex 9a.

M. Yuan et al. / Journal of Organometallic Chemistry 696 (2011) 905e912
909
PhPh
P
Ph Ph
H
N
N
N
P
NCCH3
NCCH3
R
10
Pd
Pd
Pd
ClO4
R
R
P
P
Ph Ph
H
H
PhPh
ClO4
6
ClO4
5
11
R-
PhPh
P
Ph Ph
P
H
N
N
N
R
NCCH3
NCCH3
10
Pd
Pd
Pd
P
P
Ph Ph
PhPh
ClO4
11
ClO4
13
ClO4
12
S-
a: R=CN
b
: R=CHO
c: R=CH2OH
Scheme 4.
prior to use when necessary. NMR spectra were recorded at 25 ꢁC on
Bruker ACF 400 (1H at 400 MHz,13C at 100 MHz, and 31P at 162 MHz)
and 500 (1H at 500 MHz, 13C at 126 MHz, and 31P at 202 MHz)
48.4 (d, JPC ¼ 2.0 Hz), 51.2 (d, JPC ¼ 2.9 Hz), 73.0 (d, JPC ¼ 3.1 Hz), 103.3
(d, JPC ¼ 12.2 Hz), 117.1 (d, JPC ¼ 4.6 Hz), 123.3 (s), 124.3 (s), 124.9 (d,
JPC ¼ 6.0 Hz), 125.9 (s), 128.5 (d, 2C, JPC ¼ 10.6 Hz), 128.6
(d, JPC ¼ 45.3 Hz), 128.6 (s), 128.8 (s), 128.9 (d, JPC ¼ 43.7 Hz), 129.2 (d,
2C, JPC ¼ 10.7 Hz), 131.1 (s), 131.2 (d, JPC ¼ 2.3 Hz), 131.6 (d,
JPC ¼ 2.4 Hz), 133.9 (d, 2C, JPC ¼ 11.2 Hz), 134.0 (d, 2C, JPC ¼ 12.2 Hz),
135.3 (d, JPC ¼ 12.4 Hz), 148.9 (d, JPC ¼ 4.5 Hz), 149.2 (d, JPC ¼ 2.0 Hz),
149.3 (s).
spectrometers. Chemical shifts (d) are reported in parts per million.
Proton and carbon chemical shifts are relative to the residual solvent
peaks. Coupling constants are reported in hertz. Optical rotations
were measured on the specified solution in a 0.1 dm cell at 20 ꢁC
with a PerkineElmer 341 polarimeter. Elemental analyses were
performed by the Elemental Analysis Laboratory of the Division of
Chemistry and Biological Chemistry at Nanyang Technological
University. Melting points were measured using the SRS Optimelt
Automated Melting Point System, SRS MPA100.
The chiral palladium templates R-2 [57,58], R-11, and S-11 [59]
were prepared according to literature methods.
Caution! Perchlorate salts of metal complexes are potentially
explosive compounds and should be handled with care.
The mother liquor was concentrated, and recrystallized from
benzene and n-pentane to afford the cis-isomer cis-R-3 as yellowish
needles. cis-R-3 (0.70 g, 32.6%), [
a
]D ¼ þ146.7ꢁ (c 0.9, CH2Cl2). Mp:
133e135 ꢁC. Anal. Calcd for C30H30ClN2PPd: C, 60.9; H, 5.1; N, 4.7.
Found: C, 60.6; H, 5.2; N, 4.9. 31P NMR (CDCl3, 202 MHz):
NMR (CDCl3, 500 MHz):
2.02 (d, 3H, JHH ¼ 6.4 Hz, CHMe), 2.74 (d,
3H, JPH ¼ 1.4 Hz, NMe), 2.98 (d, 3H, JPH ¼ 3.5 Hz, NMe), 3.52 (ddd, 1H,
d
32.5 (s).1H
d
JHH ¼ 10.2 Hz,
JHH ¼ 12.4 Hz,
PCH0H),
4.08
(ddd,
1H,
JHH ¼ 5.9 Hz, JHH ¼ 12.4 Hz, JPH ¼ 1.4 Hz PCH0H), 4.37 (qn, 1H, JHH
3.1. Preparation of monophosphine palladium complex R-3
Sodium diphenylphosphide solution, prepared by reaction of
diphenylphosphine (0.80 g, 4.30 mmol) with sodium (0.11 g,
4.8 mmol) in THF (25 mL), was cooled to 0 ꢁC, and bromoacetalde-
hyde dimethylacetal (0.73 g, 4.30 mmol) in THF (5 mL) was added
dropwise within 5 min. The resulting mixture was stirred for 1 h at
room temperature, and 4 N HCl (15 mL) was added and stirred for
10 h. The mixture was basified with sodium carbonate until the pH
value was 10, and was subsequently extracted with ethyl acetate
(3 ꢂ 20 mL). To the combined organic phases, (triphenylphosphor-
anylidene)-acetonitrile (1.81 g, 6.02 mmol)) was added. The
mixture was stirred for 2 h at room temperature, and palladium
dimer R-2 (1.46 g, 2.15 mmol) was added, and stirred for another 1 h.
Upon removal of the solvent, the residue was purified by column
chromatography on silica gel (EtOAc/Hexanes ¼ 1:3) to afford the
product R-3 as a pale yellow powder (cis/trans ¼ 1:1.6, 2.15 g, 85%).
The trans-isomer trans-R-3 could be isolated for characterization
by fractional crystallization from ethyl acetate and hexanes as
yellowish square crystals. trans-R-3 (1.10 g, 51.2%), [
a
]D ¼ ꢀ55.4ꢁ (c
0.8, CH2Cl2). Mp: 198e201 ꢁC. Anal. Calcd for C30H30ClN2PPd: C, 60.9;
H, 5.1; N, 4.7. Found: C, 60.6; H, 5.2; N, 4.9. 31P NMR (CDCl3, 202 MHz):
d
33.7 (s). 1H NMR (CDCl3, 500 MHz):
d
2.06 (d, 3H, JHH ¼ 6.4 Hz,
CHMe), 2.70 (s, 3H, NMe), 2.98(d, 3H, JPH ¼ 3.4 Hz, NMe), 3.17(ddd,1H,
JHH ¼ 9.0 Hz, JHH ¼ 12.2 Hz, PCH0H), 4.03 (ddd, 1H, JHH ¼ 7.2 Hz,
JHH ¼ 12.2 Hz, PCH0H), 4.36 (qn, 1H, JHH ¼ JPH ¼ 6.2 Hz, CHCH3), 5.17
(dd, 1H, JHH ¼ 16.4 Hz, JPH ¼ 4.8 Hz, CHCN), 6.61e8.11 (m, 17H, Ar and
PCH2CH).13C NMR (CDCl3,100 MHz):
d
23.8 (s), 36.8 (d, JPC ¼ 29.2 Hz),
Fig. 3. Molecular structure and absolute stereochemistry of complex 9c.

910
M. Yuan et al. / Journal of Organometallic Chemistry 696 (2011) 905e912
Table 3
slow diffusion of diethyl ether into the acetonitrile solution as an
off-white solid.
ꢁ
ꢀ
Selected bond lengths (A) and angles ( ) of 9c.
Pd1eP1
Pd1eP2
C13eP1
C16eP2
Cl2ePd1eCl1
P2ePd1eCl2
P2ePd1eCl1
2.234(2)
2.226(2)
1.861(7)
1.841(7)
91.7(1)
Pd1eCl1
Pd1eCl2
C13eC16
P2ePd1eP1
P1ePd1eCl1
P1ePd1eCl2
P1eC13eC16
2.358(2)
2.345(2)
1.536(9)
86.1(1)
92.0(1)
176.4(1)
107.9(4)
3.3. Preparation of the formyl-functionalized complexes 5b and 6b
and the dichloro palladium complexes 9b
To a solution of regioisomers 5a and 6a (0.4 g, 0.48 mmol) in
dichloromethane (15 mL) was added DIBAL-H (1 M in heptane,
2.0 mL, 2.0 mmol) at ꢀ78 ꢁC. After being stirred for 6 h, the mixture
quenched with water (2 mL), warmed to 0 ꢁC, and then treated with
H2SO4 acid (0.5 M, 20 mL). The organic phase was separated, washed
with H2O (3 ꢂ 20 mL), and concentrated. The residue was purified
by flush column chromatography on silica (CH2Cl2/acetone/
hexanes ¼ 2:1:1) to give the regioisomers 5b and 6b as a pale yellow
90.3(1)
177.1(1)
¼ JPH ¼ 6.2 Hz, CHCH3), 5.24 (dd, 1H, JHH ¼ 11.0 Hz, JPH ¼ 3.7 Hz,
CHCN), 6.63e8.17 (m, 17H, Ar and PCH2CH). 13C NMR
(CDCl3, 126 MHz):
d
23.9 (s), 36.3 (d, JPC ¼ 30.8 Hz), 48.4 (s), 51.3 (d,
JPC ¼ 2.8 Hz), 72.9 (d, JPC ¼ 3.0 Hz), 101.6 (d, JPC ¼ 12.0 Hz), 115.4
(d, JPC ¼ 4.5 Hz), 123.2 (s), 124.3 (s), 124.9 (d, JPC ¼ 5.7 Hz), 125.8 (s),
128.3 (d, JPC ¼ 45.4 Hz),128.5 (d, 2C, JPC ¼ 10.7 Hz),128.7 (s),128.8 (s),
128.9 (d, JPC ¼ 44.0 Hz), 129.2 (d, 2C, JPC ¼ 10.6 Hz), 131.2 (s), 131.2 (d,
JPC ¼ 2.9 Hz), 131.6 (d, JPC ¼ 2.0 Hz), 134.1 (d, 2C, JPC ¼ 12.1 Hz), 134.2
(d, 2C, JPC ¼ 11.2 Hz), 135.4 (d, JPC ¼ 12.6 Hz), 148.6 (d, JPC ¼ 2.0 Hz),
148.9 (s), 149.1 (d, JPC ¼ 1.6 Hz).
solid (0.34 g, 85%). 31P NMR (CDCl3, 202 MHz):
d 30.9 (d,
JPP ¼ 32.3 Hz), 45.7 (d, JPP ¼ 33.6 Hz), 51.3 (d, JPP ¼ 33.6 Hz), 65.5 (d,
JPP ¼ 32.3 Hz).
A solution of 5b and 6b (0.34 g, 0.40 mmol) in dichloromethane
(8 mL) wastreated with concentrated hydrochloric acid(5 mL) for 3 h
at room temperature. The mixture was then washed with water
(3 ꢂ 20 mL), concentrated. The residue was purified by column
chromatography on silica (CH2Cl2/acetone/hexanes ¼ 6:2:3) to afford
product 9b as a white solid (0.22 g, 87%). [
a
]D ¼ þ52.5ꢁ (c 0.8, CH2Cl2).
3.2. Hydrophosphination of complex R-3 and preparation of the
diiodo complex 9a
Mp: 270e272 ꢁC (decomp.). Anal. Calcd for C28H26Cl2OP2Pd: C, 54.4;
H, 4.2. Found: C, 54.2; H, 4.3. 31P NMR (CD2Cl2, 202.4 MHz):
d 52.9 (d,
JPP ¼ 6.5 Hz), 71.4 (d, JPP ¼ 6.5 Hz). 1H NMR (CD2Cl2, 500 MHz):
A dichloromethane (15 mL) solution of cis-R-3 (0.50 g, 0.84 mmol)
was treated with AgClO4$H2O (0.28 g,1.27 mmol) in water (3 mL) for
1 h at room temperature. The organic layer, upon the removal of AgCl
precipitate, was washed with H2O (3 ꢂ 20 mL), concentrated and
redissolved in dichloromethane (15 mL). The solution was then
treated with diphenylphosphine (0.16 g, 0.84 mmol) in dichloro-
methane (4 mL) and triethylamine (0.13 g, 1.27 mmol) at ꢀ78 ꢁC for
2 h. The solvent was removed under reduced pressure. The crude
product was purified by chromatography on silica (CH2Cl2/acetone/
hexanes ¼ 2:1:2) to afford a mixture of regioisomers 5a and 6a as off-
d
1.98e2.08 (m, 1H, JHH ¼ 12.2 Hz, JHH ¼ 14.6 Hz, PCHH0), 2.31e2.38
(m,1H, JHH ¼ 10.6 Hz, JHH ¼ 19.0 Hz, CHH0CHO), 2.71e2.76 (dd, br,1H,
JHH ¼ 2.7 Hz, JHH ¼ 19.0 Hz, CHH0CHO), 2.85e3.01 (dddd, 1H,
JHH ¼ 4.9 Hz, JHH ¼ 14.6 Hz, JPH ¼ 15.0 Hz, JPH ¼ 49.4 Hz, PCHH0),
3.24e3.35 (m, 1H, PCH0), 7.49e8.10 (m, 20H, Ar), 9.47 (t, 1H,
JPH ¼ 5.6 Hz, CHO). 13C NMR (CD2Cl2, 126 MHz):
d 32.4 (dd,
JPC ¼ 16.4 Hz, JPC ¼ 35.1 Hz), 33.5 (dd, JPC ¼ 16.0 Hz, JPC ¼ 32.3 Hz),
43.5 (d, JPC ¼ 14.7 Hz), 124.8 (d, JPC ¼ 51.4 Hz), 125.9 (d, JPC ¼ 54.0 Hz),
126.7 (d, JPC ¼ 53.9 Hz), 128.9 (d, 2C, JPC ¼ 11.8 Hz), 129.1 (d, 4C,
JPC ¼ 11.0 Hz), 129.2 (d, JPC ¼ 55.6 Hz), 129.4 (d, 2C, JPC ¼ 10.9 Hz),
132.2 (d, JPC ¼ 2.9 Hz), 132.3 (d, JPC ¼ 3.1 Hz), 132.4 (d, JPC ¼ 2.6 Hz),
133.1 (d, JPC ¼ 2.5 Hz), 133.2 (d, 2C, JPC ¼ 9.6 Hz), 133.4 (d, 2C,
JPC ¼ 11.1 Hz), 133.7 (d, 2C, JPC ¼ 11.0 Hz), 136.0 (d, 2C, JPC ¼ 12.0 Hz),
197.9 (d, JPC ¼ 10.0 Hz).
white solid (0.64 g, 90%). 31P NMR (CDCl3, 202):
d 28.7 (d,
JPP ¼ 33.5 Hz), 43.5 (d, JPP ¼ 33.8 Hz), 49.1 (d, JPP ¼ 33.8 Hz), 62.4 (d,
JPP ¼ 33.5 Hz).
A solution of regioisomers 5a and 6a (0.4 g, 0.48 mmol) in
dichloromethane (8 mL) was stirred vigorously with concentrated
hydrochloric acid (6 mL) and NaI (0.25 g, 1.64 mmol) at room
temperature for 12 h. The mixture was washed with water
(3 ꢂ 20 mL), concentrated, and purified by column chromatography
on silica (CH2Cl2/acetone ¼ 12:1). Upon crystallization in dichlor-
omethaneediethyl ether, product 9a was isolated as red cubic
3.4. Preparation of the hydroxyl-functionalized complexes 5c and
6c and the dichloro palladium complexes 9c
To a solution of regioisomers 5b and 6b (generated from 5a and
6a, 0.40 g, 0.48 mmol) in dichloromethane (15 mL) was added
DIBAL-H (1 M in heptane, 1.8 mL, 1.8 mmol) at ꢀ78 ꢁC. The mixture
was stirred for 2 h at ꢀ78 ꢁC, quenched with water (2 mL), warmed
to 0 ꢁC, and H2SO4 acid (0.5 M,15 mL) was added. The organic phase
was separated, washed with H2O (3 ꢂ 20 mL), and concentrated. The
residue was purified by flush column chromatography on silica
(CH2Cl2/acetone/hexanes ¼ 2:1:1) to give the regioisomers 5c and
6c as a pale yellow solid (0.29 g, 72%). 31P NMR (CDCl3, 202 MHz):
crystals (0.36 g, 94%). [
a
]
¼ þ58.2ꢁ (c 0.6, CH2Cl2). Mp: 356e358 ꢁC
D
(decomp.). Anal. Calcd for C28H25I2NP2Pd: C, 42.2; H, 3.2. Found: C,
42.0; H, 3.4. 31P NMR (CD2Cl2, 202 MHz):
d
43.7 (d, JPP ¼ 12.0 Hz),
61.7 (d, JPP ¼ 12.0 Hz). 1H NMR (CD2Cl2, 500 MHz):
d 2.17e2.24 (m,
1H, JHH ¼ 10.6 Hz, JHH ¼ 16.9 Hz, CHH0CN), 2.31e2.41 (m, 1H, JHH
¼ 12.7 Hz, JHH ¼ 14.5 Hz, PCHH0), 2.48e2.53 (dt, 1H, JHH ¼ 4.5 Hz,
JHH ¼ 16.9 Hz, JPH ¼ 4.5 Hz, CHH0CN), 2.68e2.84 (m, 1H,
JHH ¼ 4.7 Hz, JHH ¼ 14.5 Hz, PCHH0), 2.82e2.88 (m, 1H, PCH0),
d
31.2 (d, JPP ¼ 33.4 Hz), 47.3 (d, JPP ¼ 33.5 Hz), 52.4 (d, JPP ¼ 33.5 Hz),
7.52e8.03 (m, 20H, Ar). 13C NMR (CD2Cl2, 126 MHz):
d
18.2 (d,
66.2 (d, JPP ¼ 33.4 Hz).
JPC ¼ 22.0 Hz), 34.8 (dd, JPC ¼ 18.1 Hz, JPC ¼ 33.3 Hz), 37.2 (dd,
JPC ¼ 20.1 Hz, JPC ¼ 26.7 Hz), 118.1 (d, JPC ¼ 9.3 Hz), 125.1 (d, JPC
¼ 48.3 Hz), 127.8 (d, JPC ¼ 52.5 Hz), 128.1 (d, JPC ¼ 52.2 Hz), 129.1 (d,
4C, JPC ¼ 11.3 Hz), 129.5 (d, 2C, JPC ¼ 11.2 Hz), 129.6 (d, 2C,
JPC ¼ 11.1 Hz), 131.4 (d, JPC ¼ 56.6 Hz), 132.2 (br), 132.5 (br), 133.0
(br),133.4 (br), 133.6 (d, 2C, JPC ¼ 10.4 Hz), 133.8 (d, 2C, JPC ¼ 9.4 Hz),
135.1 (d, 2C, JPC ¼ 11.3 Hz), 136.6 (d, 2C, JPC ¼ 12.1 Hz).
A solution of 5c and 6c (0.29 g, 0.34 mmol) in dichloromethane
(8 mL) was treated with concentrated hydrochloric acid (5 mL) for
3 h at room temperature. The mixture was then washed with water
(3 ꢂ 20 mL), concentrated, and was purified by column chroma-
tography on silica (CH2Cl2/acetone/hexanes ¼ 3:1:1). Upon crystal-
lization from dichloromethane-diethyl ether, product 9c was
isolated as colorless square crystals (0.18 g, 86%). [
a
]D ¼ þ51.9ꢁ (c 0.5,
The same procedure was adopted for the hydrophosphination of
trans-R-3. The regioisomers 5a and 6a could be isolated by a slow
chromatography on silica (CH2Cl2/acetone/hexanes ¼ 2:1:2), or by
CH2Cl2). Mp: 266e268 ꢁC (decomp.). Anal. Calcd for
C28H28Cl2OP2Pd: C, 54.3; H, 4.6. Found: C, 54.1; H, 4.8. 31P NMR
(CD2Cl2, 202 MHz):
d
51.6 (d, JPP ¼ 5.8 Hz), 72.0 (d, JPP ¼ 5.8 Hz). 1H

M. Yuan et al. / Journal of Organometallic Chemistry 696 (2011) 905e912
911
NMR (CD2Cl2, 500 MHz):
d
1.28e1.34 (m, 1H, CHH0CH2OH), 1.60 (br,
d
1.77 (br, 1H, JHH ¼ 5.6 Hz, CH2OH), 1.87e2.00 (m, 3H, CH2CH2OH
1H, CH2OH), 1.87e1.93 (m, 1H, PCHH0), 2.00e2.10 (m, 1H,
and PHH0), 2.25e2.31 (m, 1H, PHH0), 2.36e2.43 (m, 1H, PCHCH2),
3.73e3.77 (m, 2H, CH2OH), 7.22e7.42 (m, 20H, Ar).
JHH ¼ JHH ¼ 13.9 Hz,
CHH0CH2OH),
2.88e3.06
(dddd,
1H,
JHH ¼ 4.9 Hz, JHH ¼ 14.7 Hz, JPH ¼ 12.6 Hz, JPH ¼ 55.7 Hz, PCHH0),
3.02e3.09 (m, 1H, PCHCH2), 3.48e3.54 (m, 1H, CHH0OH), 3.58e3.63
(m, 1H, CHH0OH), 7.48e8.07 (m, 20H, Ar). 13C NMR (DMSO-d6,
3.6. X-ray crystal structure determinations of complexes trans-R-3,
9a and 9c
100 MHz):
d
31.9 (dd, JPC ¼ 15.6 Hz, JPC ¼ 35.6 Hz), 30.0 (dd,
JPC ¼ 3.8 Hz, JPC ¼ 17.6 Hz), 36.7 (dd, JPC ¼ 13.2 Hz, JPC ¼ 32.5 Hz),
59.3 (d, JPC ¼ 9.7 Hz), 125.6 (d, JPC ¼ 50.5 Hz),127.3 (d, JPC ¼ 53.3 Hz),
127.7 (d, JPC ¼ 52.7 Hz), 129.2 (d, 2C, JPC ¼ 11.4 Hz), 129.3 (d, 2C,
JPC ¼ 10.8 Hz), 129.4 (d, 2C, JPC ¼ 11.0 Hz), 129.7 (d, 2C, JPC ¼ 11.2 Hz),
130.2 (d, JPC ¼ 56.2 Hz), 132.3 (d, JPC ¼ 2.4 Hz), 132.4 (d, JPC ¼ 2.4 Hz),
132.8 (d, JPC ¼ 2.2 Hz), 133.0 (d, JPC ¼ 2.4 Hz), 133.6 (d, 2C,
JPC ¼ 10.7 Hz), 133.7 (d, 2C, JPC ¼ 9.3 Hz), 134.1 (d, 2C, JPC ¼ 11.0 Hz),
136.1 (d, 2C, JPC ¼ 11.5 Hz).
Crystal data and a summary of the crystallographic analyses are
given in Table 4. Diffraction data were collected on a Bruker X8 CCD
diffractometer with Mo K
SADABS absorption corrections were applied. All non-hydrogen
atoms were refined anisotropically, while the hydrogen atoms were
introduced at calculated positions and refined riding on their
carrier atoms. The absolute configurations of the chiral complexes
were determined unambiguously by using the Flack parameter.
a radiation (graphite monochromator).
3.5. Liberation of functionalized chiral 1,2-diphosphine ligands 10a,
10b, and 10c
Acknowledgement
We thank Nanyang Technological University for support of this
research and PhD scholarship to M. Y.
A solution of 9a (0.15 g, 0.19 mmol) in dichloromethane (10 mL)
was stirred vigorously with aqueous KCN (0.5 g, 7.68 mmol) for
40 min. The organic layer was separated, washed with water, and
dried with Na2SO4. The cyano-functionalized 1,2-diphosphine
ligand 10a was obtained as white solid upon removal of solvent
Appendix A. Supplementary material
CCDC 784776, 784777 and 784778 contain the supplementary
crystallographic data for complexes trans-R-3, 9c and 9a. These data
can be obtained free of charge from The Cambridge Crystallo-
graphic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.
under reduced pressure (0.078 g, 95%). [
a
]D ¼ ꢀ113.6 (c 1.3, CH2Cl2).
31P NMR (CDCl3, 202 MHz):
d
ꢀ6.0 (d, JPP ¼ 24.1 Hz), ꢀ22.8 (d,
JPP ¼ 24.1 Hz). 1H NMR (CDCl3, 500 MHz):
d
2.22e2.31 (m, 2H, PHH0
and CHH0CN), 2.34e2.39 (m, 1H, PHH0), 2.41e2.47 (m, 1H, PCHCH2),
2.94e3.02 (m, 1H, CHH0CN), 7.25e7.44 (m, 20H, Ar).
References
Similarly the formyl-functionalized 1,2-diphosphine ligand 10b
(0.098 g, 92%) was achieved from 9b (0.15 g, 0.24 mmol) as a white
[1] P.R. Auburn, P.B. Mackenzie, B. Bosnich, J. Am. Chem. Soc. 107 (1985)
2033e2046.
solid. [
d
a
]D ¼ ꢀ102.7ꢁ (c 1.1, CH2Cl2). 31P NMR (CDCl3, 202 MHz):
ꢀ1.4 (d, JPP ¼ 27.4 Hz), ꢀ22.0 (d, JPP ¼ 27.4 Hz). 1H NMR (CDCl3,
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1759e1764.
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[8] T. Nishikata, Y. Yamamoto, N. Miyaura, Chem. Lett. 36 (2007) 1442e1443.
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1569e1575.
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[12] D. Carmona, C. Cativiela, R. García-Correas, F.J. Lahoz, M.P. Lamata, J.A. López,
M.P. López-Ram de Víu, L.A. Oro, E.S. José, F. Viguri, Chem. Commun. (1996)
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2826e2832.
[14] D. Carmona, M.P. Lamata, F. Viguri, R. Rodríguez, C. Barba, F.J. Lahoz,
M.L. Martín, L.A. Oro, L. Salvatella, Organometallics 26 (2007) 6493e6496.
[15] D. Carmona, M.P. Lamata, F. Viguri, R. Rodríguez, L.A. Oro, A.I. Balana,
F.J. Lahoz, T. Tejero, P. Merino, S. Franco, I. Montesa, J. Am. Chem. Soc. 126
(2004) 2716e2717.
[16] M. Sawamura, Y. Ito, Chem. Rev. 92 (1992) 857e871.
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[19] M. Sawamura, Y. Nakayama, T. Kato, Y. Ito, J. Org. Chem. 60 (1995)
1727e1732.
[20] C.R. Landis, R.A. Sawyer, E. Somsook, Organometallics 19 (2000) 994e1002.
[21] H.-U. Blaser, C. Malan, B. Pugin, F. Spindler, H. Steiner, M. Studer, Adv. Synth.
Catal. 345 (2003) 103e151.
[22] U. Nagel, Angew. Chem., Int. Ed. Engl. 23 (1984) 435e436.
[23] K. Achiwa, J. Am. Chem. Soc. 98 (1976) 8265e8266.
[24] G.L. Baker, S.J. Fritschel, J.R. Stille, J.K. Stille, J. Org. Chem. 46 (1981)
2954e2960.
[25] Y.-Y. Yan, T.V. RajanBabu, J. Org. Chem. 65 (2000) 900e906.
[26] J. Holz, M. Quirmbach, A. Börner, Synthesis (1997) 983e1006.
[27] A. Börner, J. Ward, W. Ruth, J. Holz, A. Kless, D. Heller, H.B. Kagan, Tetrahedron
50 (1994) 10419e10430.
[28] D.K. Wicht, D.S. Glueck, in: A. Togni, H. Grutzmacher (Eds.), Catalytic Hetero-
functionalization, Wiley-VCH, Weinheim, Germany, 2001, pp. 143e170.
500 MHz):
d
2.93e2.00 (m, 1H, PHH0), 2.30e2.36 (m, 1H, PHH0),
2.62e2.69 (m, 1H, JHH ¼ 5.9 Hz, JHH ¼ 5.6 Hz, JHH ¼ 17.8 Hz,
CHH0CHO), 2.76e2.83 (m, 1H, JHH ¼ 5.9 Hz, JHH ¼ 5.4 Hz,
JHH ¼ 17.8 Hz, CHH0CHO), 2.89e2.95 (m, 1H, PCHCH2), 7.25e7.43 (m,
20H, Ar), 9.64 (br, 1H, CH2CHO).
The hydroxyl-functionalized 1,2-diphosphine 10c [27] (0.10 g,
96%) was liberated from 9c (0.15 g, 0.24 mmol) as a white solid.
[
a]
¼ ꢀ144.9ꢁ (c 0.9, CH2Cl2). 31P NMR (CDCl3, 202 MHz):
ꢀ1.0 (d,
d
D
JPP ¼ 21.2 Hz), ꢀ19.8 (d, JPP ¼ 21.2 Hz). 1H NMR (CDCl3, 500 MHz):
Table 4
Crystallographic data for complexes trans-R-3, 9a, and 9c.
trans-R-3
9a
9c
Formula
Fw
C30H30ClN2PPd
591.38
C28H25I2NP2Pd
797.63
P2(1)
Monoclinic
11.195(1)
14.993(1)
17.082(1)
90
105.4(1)
90
2764.8(2)
4
C28H28Cl2OP2Pd$CH2Cl2
704.67
P2(1)
Monoclinic
9.442(1)
8.760(1)
19.313(1)
90
96.5(1)
90
1587.2(4)
2
Space group
Cryst syst
P2(1) 2(1) 2(1)
Orthorhombic
11.282(1)
13.248(1)
18.362(1)
90
90
90
2744.5(1)
4
1.431
ꢀ
a/A
ꢀ
b/A
ꢀ
c/A
ꢁ
ꢁ
a
/
b
/
ꢁ
g
/
3
ꢀ
V/A
Z
Dcalcd/g cmꢀ3
1.916
0.71073
3.038
1.474
0.71073
1.043
ꢀ
l
/A
0.71073
0.853
m
/mmꢀ1
F(000)
1208
1528
712
Flack param
R1 (obs data)a
wR2(obs data)b
ꢀ0.027(10)
0.07(3)
0.0351
0.0777
ꢀ0.01(4)
0.0602
0.164
0.0285
0.0545
P
P
a
R1 ¼ kFoj ꢀ jFck/ jFoj.
qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
P
P
½wðFo2 ꢀ Fc2Þ2ꢃ= ½wðFo2Þ2ꢃg, wꢀ1
¼
s
2(Fo)2 þ (aP)2 þ bP.
b
wR2 ¼
f

912
M. Yuan et al. / Journal of Organometallic Chemistry 696 (2011) 905e912
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