Synthesis and application in catalysis of planar chiral (η5-Cyclohexadienyl)tricarbonylmanganese-based ligands

Article abstract of DOI:10.1021/om200231p

Mono- and bidentate ligands (5-8, 15-18, 20, 29-31) have been synthesized in which the phosphinyl group substitutes a (η⁵-cyclohexadienyl) Mn(CO)₃ scaffold. In the case of one of the bidentate ligands, 15, the formation of the corresponding Pd complex was studied. The complex unexpectedly afforded two bimetallic complexes depending on the solvent of the reaction: the neutral complex 33 and the cationic complex 34, whose X-ray structures were established. The catalysts carrying the new ligands demonstrated high activity (99% conversion) in the palladium-catalyzed allylic substitution. The resolution of three of the ligands, 6, 8, and 15, was achieved, and the catalyst with the enantioenriched P-N ligand 15 delivered fairly good enantioselectivity in asymmetric allylic substitution.

Full text of DOI:10.1021/om200231p

ARTICLE
pubs.acs.org/Organometallics
Synthesis and Application in Catalysis of Planar Chiral
(η5-Cyclohexadienyl)tricarbonylmanganese-Based Ligands
Franc-oise Rose-Munch,*,† Derya Cetiner,† Murielle Chavarot-Kerlidou,† Eric Rose,*,†
Francine Agbossou-Niedercorn,‡ Lise-Marie Chamoreau,§ and Geoffrey Gontard§
†UPMC Univ Paris 6, Institut Parisien de Chimie Molꢀeculaire, CNRS UMR 7201, Equipe Chimie Organique and Organomꢀetallique,
4 place Jussieu, 75005 Paris Cedex 05, France
‡USTL, ENSCL, CNRS UMR 8181, 59655 Villeneuve d’Ascq, France
§UPMC Univ Paris 6, Institut Parisien de Chimie Molꢀeculaire, CNRS UMR 7201, Centre de Rꢀesolution de Structures, 4 place Jussieu,
75005 Paris Cedex 05, France
S Supporting Information
b
ABSTRACT: Mono- and bidentate ligands (5ꢀ8, 15ꢀ18, 20,
29ꢀ31) have been synthesized in which the phosphinyl group
substitutes a (η5-cyclohexadienyl)Mn(CO)3 scaffold. In the
case of one of the bidentate ligands, 15, the formation of the
corresponding Pd complex was studied. The complex unex-
pectedly afforded two bimetallic complexes depending on the
solvent of the reaction: the neutral complex 33 and the cationic
complex 34, whose X-ray structures were established. The
catalysts carrying the new ligands demonstrated high activity (99% conversion) in the palladium-catalyzed allylic substitution.
The resolution of three of the ligands, 6, 8, and 15, was achieved, and the catalyst with the enantioenriched PꢀN ligand 15 delivered
fairly good enantioselectivity in asymmetric allylic substitution.
complexes in catalysis. To our knowledge, up to now, very few η5
1. INTRODUCTION
complexes substituted by a PPh2 function have been synthesized.
Whereas planar chiral ferrocenes are the best-known examples
The introduction of a phosphinyl group at the sp3 C6 carbon of
of organometallic ligands for metal-catalyzed asymmetric
the cyclohexadienyl unit, which is located exo to the Mn(CO)3
reactions,1a tricarbonylmetal-containing chiral complexes are now
tripod, has been realized by addition of PPh2Li onto the cationic
beginning to play major roles in enantioselective catalysis.1b In
(η6-benzene)Mn(CO)3þ complex17 (complex A, Figure 1). Two
such nonmetallocenic structures, the “spectator” organometallic
other phosphine derivatives, with the phosphinyl substituent
fragment not only generates the planar chirality in the catalytic
localized on the C1 carbon (complexes B) or on the C2 carbon
center environment but may also act as a steric and electronic
(complex C) of the cyclohexadienyl moiety, were obtained from
modulator.2 Most of the examples described in the literature rely
a chloro-substituted precursor by a palladium-catalyzed cross-
on a planar chiral (η6-arene)Cr(CO)3 scaffold.3ꢀ5 Other ligands
coupling procedure for B18 or from a bromo derivative19 by a halogenꢀ
based on a different tricarbonylmetal tripod are relatively rare and,
metal exchange reaction for C.20 Finally, a fourth example
to our knowledge, are limited to (η5-Cp)Re(CO)3 (cyrhetrene)
(complex D) was recently prepared from an anisole derivative
derivatives,6ꢀ8 to a single example with a (η4-diene)Fe(CO)3
submitted to a lithiationꢀelectrophilic quenching sequence.20
fragment,9 and to (η5-Cp)Mn(CO)3.10ꢀ14 The latter compounds
To take advantage of the synthesis of the η5 complexes BꢀD
containing a cyclopentadienyl platform are the only tricarbonyl-
substituted on the π system, it was interesting to generalize
manganese complexes used as catalysts. Mn complexes such as
the three main methods of functionalization of η5 Mn complexes
(η5-cyclohexadienyl)Mn(CO)3 complexes, which could lie some-
(Pd cross-coupling reactions,18,21 lithiationꢀelectrophilic
where between the (η6-arene)Cr(CO)3 and the cymantreneseries,
quenching sequence,22 and metalꢀhalogen exchange followed
have never been employed for the design of planar chiral ligands.
by electrophilic trapping19) to the preparation of other examples
We thought that their originality due, in part, to their special
of monodentate ligands, in particular phosphinyl-substituted η5
structure with an sp3 carbon lying above the plane of the π
complexes with a phenyl group on the sp3 carbon atom. More-
system15 as well as electronic properties very close to those of
over, it was of interest to try the combination of the different
(arene)Cr(CO)3 complexes16 might confer them interesting
functionalization pathways developed by our group in order to
properties as ligands in catalysis.
The easy introduction of chelating functions on the η5 scaffold,
such as a PPh2 phosphinyl group, is thus of strategic importance for
Received: March 16, 2011
Published: June 15, 2011
the developmentof applications of (η5-cyclohexadienyl)Mn(CO)3
r
2011 American Chemical Society
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Table 1. Phosphinylation Conditions for Complexes 1 and 2
entry
substrate
R1
R2
product
yield (%)
C2:C3
1
2
1a
2c
H
H
H
5a,b
43b
83
70:30
C3 only
Figure 1. Previous PPh2-substituted (η5-cyclohexadienyl)Mn(CO)3
complexes.
OMe
6
a Conditions: 2 equiv of nBuLi, 2 equiv of TMEDA, reaction time 2 h,
then 2.5 equiv of Ph2PCl. b Conversion 70%. c Conditions: 1.6 equiv of
nBuLi, 1.6 equiv of TMEDA, reaction time 1 h, then 2 equiv of Ph2PCl.
Scheme 1. Phosphinylation Conditions for Complexes 3
and 4
Figure 2. Monodentate phosphorus ligands and the corresponding
(η5-cyclohexadienyl)Mn(CO)3 starting complexes.
Figure 3. Bidentate ligands developed in this study.
achieve the regioselective introduction of various chelating groups
around the η5 scaffold, to give a new family of potential bidentate
ligands.
In this paper, we wish to report the synthesis of a large variety
of mono- and bidentate ligands built on diversely substituted (η5-
cyclohexadienyl)Mn(CO)3 complexes, the coordination proper-
ties of some of them, and their application in enantioselective
catalysis. Part of this work has been the subject of a preliminary
communication.23
involves the presence of ortho-directing groups such as a methoxy
or a chloride group on the substrate; method A) or by a halogenꢀ
metal exchange (for the brominated substrates; method B).
Starting from complex 1, lithiation by nBuLi followed by
electrophilic quenching with PPh2Cl under the same experi-
mental conditions as those described for other electrophiles22
provided the two regioisomers 5a,b, which were isolated in a
C2:C3 ratio of 70:30 (Table 1, entry 1).
When complex 2 was reacted under identical conditions, only
the regioisomer 6, substituted ortho to the methoxy group, was
obtained23 (Table 1, entry 2). No C1 deprotonation was observed
during the synthesis of 5 and 6, in good agreement with what was
already known.22
To functionalize the terminal positions, we used bromo-
substituted complexes as starting materials. The halogenꢀmetal
exchange in bromo complexes 3 and 4 was realized by following
the procedure recently described.19 These conditions allowed us
to introduce a phosphinyl group at the C2 carbon of 7 and at the
2. RESULTS AND DISCUSSION
2.1. Synthesis of Monodentate Phosphorus-Based Li-
gands. With the manganese complexes 1ꢀ4 as starting materi-
als, the synthesis of monodentate phosphorus-based ligands 5ꢀ8
gathered in Figure 2 relies on a lithiationꢀelectrophilic quench-
ing sequence, using PPh2Cl as the electrophile. Depending on
the position which has to be functionalized, the lithiation was
performed either by a regioselective “direct” deprotonation (which
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Table 2. Two Consecutive LithiationꢀElectrophilic Quenching Sequences Applied to Complex 2
entry
E1X
E1
product
yield (%)
70
E2X
(CH2)2I2
E2
product
yield (%)
1
2
3
4
5
6
7
8
Ph2(O)PCl
P(O)Ph2
9
I
11
12
13
14
15
16
17
18
37
<5
95
94
84
71
80
51
Ph2PCl
PPh2
H2CdNMe2þIꢀ
CH2NMe2
10
77
Me3SiCl
(CH2)2I2
Ph2PCl
SiMe3
I
PPh2
PhSSPh
SPh
DMF
H2CdNMe2þIꢀ
CH2OHa
CH2NMe2
a After reduction by NaBH4 of the formyl complex obtained in 74% yield from the reaction of 10 with DMF.
C1 carbon of 8 (Scheme 1). This method is, therefore, a clearly
acceptable solution to easily introduce a PPh2 group on the one
side at one end of the π system that is impossible to reach using a
deprotonation procedure and on the other side at a position meta
to the methoxy group which usually orients deprotonation at an
adjacent carbon.
Scheme 2. Synthesis of Complex 20
2.2. Synthesis of Bidentate Ligands. Two synthetic strate-
gies have been developed to access the bidentate structures 15ꢀ
18, 20, and 29ꢀ31 reported in Figure 3. The first was based on
the sequence of two consecutive lithiation/electrophilic quench-
ing reactions, the regioselectivity being controlled during the
course of the first lithiation either by an ortho-directing group or
by a halogenꢀmetal exchange. The second relied on the use of
the substrate (η5-1-chloro-4-methoxy-6-phenylcyclohexadienyl)-
Mn(CO)3 (21), the chloro atom being ortho-activating for the
first functionalization through a lithiationꢀelectrophilic quench-
ing sequence and then a reacting group for the second functio-
nalization through a palladium-catalyzed coupling reaction.
2.2.1. Two LithiationꢀElectrophilic Quenching Sequences.
Typically, the functionalization of 2 was performed using 1.6 equiv
of nBuLi and TMEDA at ꢀ78 °C as previously optimized,22
followed by quenching by the appropriate electrophile. For the
first sequence, we applied electrophiles that have never been used
so far in this series: Ph2P(O)Cl and the Eschenmoser salt
H2CdN(Me)2þIꢀ (Table 2). The resulting complexes 9 and
10, regioselectively functionalized at C3 by a phosphine oxide
and a (dimethylamino)methyl group, were isolated in 70% and
77% yields, respectively (Table 2, entries 1 and 3).
Figure 4. ORTEP view of complex 15 (with thermal ellipsoids at the
30% probability level). Selected bond lengths (Å) and angles (deg):
C2ꢀP = 1.892(3), C3ꢀC8 = 1.519(5); C2ꢀPꢀC11 = 100.37(15), C11ꢀ
PꢀC17 = 101.15(15), C17ꢀPꢀC2 = 100.11(15), C3ꢀC8ꢀN = 11.8(3).
We thought next to investigate whether the phosphine oxide24
and the (dimethylamino)methyl25 groups in complexes 9 and 10,
respectively, could act as activating groups, in order to further
functionalize the cyclohexadienyl moiety. The first attempts with
complex 9 were disappointing. Indeed, despite the isolation of an
iodo-functionalized complex in 37% yield (entry 1), we failed to
introduce a phosphinyl group at the C4 position (entry 2). Classical
lithiation conditions were then applied to complex 10, using first
trimethylsilyl chloride and diiodoethane as electrophiles. The
corresponding silyl and iodo complexes 13 and 14 were isolated
in excellent yields (entries 3 and 4). Regioselective functionaliza-
tion was unambiguously confirmed by the disappearance of the
H4 proton signal at 5.05 ppm in 10, together with a downfield
shift of the H5 proton signals. This approach was next extended
to the synthesis of complexes 15ꢀ18 by using Ph2PCl, PhSSPh,
DMF, and H2CdN(Me)2þIꢀ as the second electrophiles. The
expected complexes, functionalized at C4 by diphenylphosphine,
thioether, aldehyde, and dimethylamino groups, were isolated in
good yields (entries 5ꢀ8).
The strategy to prepare complex 20, a regioisomer of 15
(Scheme 2), involved the bromo-substituted complex 3 as the
starting material. Halogenꢀmetal exchange followed by reaction
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Table 3. Selected Bond Lengths (Å) and Dihedral Angles
(DA (deg): (C1C6C5)/(C1C2C3C4C5)) for Complexes 15,
33, 34, and 38, Related to the η5 Mn(CO)3 Scaffold
Table 4. Synthesis of Bidentate Structures from 21 by
LithiationꢀElectrophilic Quenching Followed by a Palla-
dium-Catalyzed Stille Coupling
complexes
15
33
34
38
MnꢀC1
MnꢀC2
MnꢀC3
MnꢀC4
MnꢀC5
DA
2.208(3)
2.163(2)
2.158(3)
2.195(3)
2.228(3)
41.1(2)
2.214(2)
2.172(2)
2.187(2)
2.200(2)
2.222(2)
41.1(2)
2.194(3)
2.154(2)
2.165(2)
2.207(3)
2.245(3)
41.6(2)
2.327(2)
2.165(2)
2.119(3)
2.169(3)
2.152(3)
35.44(15)
entry
EX
E
product yield (%)a product yield (%)
1
2
3
4
5
DMF
CHO
C(OH)Ph2 2322b
SPh
2422b
2222c
49b
44c
48d
44e
60f
27
28
29
30
31
85
50
89
83
86
with the Eschenmoser salt gave rise to the regioselective forma-
tion of complex 19. After lithiation followed by trapping with
PPh2Cl, complex 20 was obtained with complete regioselectivity
in 51% yield (Scheme 2). It is worth noting that complexes 11ꢀ18
and 20 are the first examples of (η5-cyclohexadienyl)Mn deriva-
tives with a trisubstituted π system. Thus, it was interesting to
figure out how their structures could manage the steric arrange-
ment of the 2,3,4-substituted η5 complexes.
Ph2CO
PhSSPh
H2CdNMe2þIꢀ CH2NMe2 25
Ph2PCl PPh2
2627
a In all cases, the formation of the C3 regioisomers was detected after the
first step of lithiationꢀelectrophilic quenching in the isolated yields
noted in footnotes bꢀf. b Yield 42%. c Yield 20%. d Yield 20%. e Yield 4%.
f Yield 25%.
Yellow crystals of 15 suitable for an X-ray diffraction study26
were easily obtained by slow evaporation of a diethyl ether/pentane
solution of the complex, and an ORTEP view is shown in Figure 4.
The usual geometry of the η5-cyclohexadienyl ring is observed
with five coplanar sp2 atoms and a value of 41.1(2)° for the dihedral
angle of the (C1C2C3C4C5) and (C5C6C1) planes; thus, the η5
scaffold does not seem to be affected by the presence of sterically
demanding groups (Table 3). The dimethylamino substituent
lies in the direction opposite the Mn tripod as well as one of the
phenyl ring of the phosphine, and the methoxy group is almost in
the plane of the five carbon atoms of the π system, in the
direction opposite the amine.
Scheme 3. Coordination of Phosphorus Ligand 6 to [Pd(η3-
allyl)Cl]2
of palladium. This precursor is known to react not only with
bidentate ligands but also with monodentate ligands, such as mono-
phosphines28 or heterocyclic carbenes,29,30 forming monomeric
complexes via chloride bridge splitting. We used a protocol adapted
from the literature for the preparation of [Pd(η1-allyl)(PCy3)Cl].28
Thus, complex 6 was reacted with the dimeric palladium source
[Pd(η3-allyl)Cl]2 in Et2O at ꢀ78 °C (Scheme 3), providing the
expected monomeric derivative 32 in 63% isolated yield, which was
fully characterized.23
2.2.2. LithiationꢀElectrophilic Quenching Sequence Fol-
lowed by Palladium-Catalyzed Stille Coupling. To prepare a
series of new potential bidentate ligands, complex 2118b was chosen
as the starting derivative. Previous studies22 have shown that a
lithiationꢀelectrophilic quenching sequence leads to the formation
of two regioisomers functionalized in the positions ortho or meta
with respect to the chloride substituent. This is occurring also in the
present study with the chosen electrophiles, the isolated yield of
C3 isomers varying from 4 to 42% (Table 4). The experimental
conditions for the Stille cross-coupling reaction with 2-(tribut-
ylstannyl)thiophene (ThSnBu3) were first applied to complexes
22ꢀ24, prepared according to reported procedures,22b,c and the
reaction conditions were optimized using the new complexes 25
and 26. Thus, reaction of 22ꢀ24 with ThSnBu3 in the presence of
Pd2(dba)3ꢀAsPh3 as the catalytic system18 delivered in each case
one η5 complex substituted at the C1 position by the thienyl group
(Table 4, entries 1ꢀ3). Complexes 27ꢀ29 were isolated in 85%
and 89% yields for 27 and 29, respectively, and in a smaller 50%
yield for 28, substituted by the more sterically demanding tertiary
alcohol. We then extended these experimental conditions to the
preparation of 30 and 31, which after separation from their C3
isomers were isolated in 83 and 86% yields, respectively (entries 4
and 5).
The 31P NMR spectrum of 32 exhibits a downfield shift for the
phosphorus signal of about 40 ppm with respect to the signal
for 6, in good agreement with the ligand to metal charge density
transfer. Moreover, its crystal structure analysis23 proved unam-
biguously the coordination of the palladium center to the phos-
phine (PdꢀP bond 2.336(2) Å). The ligand coordination mode
is monodentate; no interaction between the palladium and the
OMe group is observed.
These experimental conditions could be applied with success
to the coordination of a PꢀN η5 ligand to the palladium atom.
Thus, complex 15 was reacted with [Pd(η3-allyl)Cl]2 in THF
at 40 °C and the resulting intermediate reacted with AgPF6 in
order to facilitate the PdꢀCl dissociation. Despite the presence
of this salt, the neutral bimetallic η1-allyl complex 33 was isolated
in THF, whereas when dichloromethane was useꢀd as reaction
solvent the cationic η3-allyl complex 34 with PF6 as counter-
anion was formed (Scheme 4). In both complexes 33 and 34,
2.3. Coordination Properties. Encouraged by these results,
we decided to evaluate the coordination ability of the new ligands
toward a transition metal and particularly toward palladium. The
dimeric complex [Pd(η3-allyl)Cl]2 was chosen as the source
31
the coordination of the PꢀN ligand is clearly evidenced by
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Scheme 4. Coordination of PꢀN Ligand 15 to
[Pd(η3-allyl)Cl]2
P NMR spectra, where a downfield shift of the PPh2 phophorus
signals was observed from ꢀ9.2 ppm in 15 to 32 and 31.1 ppm in
33 and 34, respectively. The observation of a signal at ꢀ142.9
ppm in the spectrum of 34 proves unambiguously the presence of
the PF6 anion.
We were lucky enough to obtain nice crystals suitable for X-ray
diffraction studies of both complexes (Figure 5, Table 3). The
allyl group of complex 3326 acts as an η1 ligand with a C33ꢀC34
bond length of 1.321(4) Å, in good agreement with a free double-
bond length. A mutually cis arrangement of η1-allyl and chloride
ligands is present, and the geometry of Pd coordination is close
to square planar, as demonstrated by the sum of all bond angles
of 360.4°. The allyl ligand is trans with respect to the nitrogen
atom. With respect to the coordination of the allyl moiety, to the
best of our knowledge, isolated Pd complexes bearing an η1-allyl
ligand are very rare.31ꢀ34 In addition, interconversion of allylic
isomers is a highrelevance in dynamics of palladium allyl complexes
and, consequently, in palladium-catalyzed allylation reactions.35,36
Indeed, it has been shown that interconversion of palladiumꢀη3-
allyl isomers occurs via an η1-allyl species.37 The structure of
complex 3426 also shows a square-planar coordination of the
palladium, but the allyl group acts as a η3 ligand, with PdꢀC
bond lengths ranging from 2.145(3) to 2.239(3) Å. As expected,
the PdꢀC(allyl) bond which is trans to the phosphorus atom is
longer (2.239(3) Å) than the PdꢀC(allyl) bond which is trans
to the nitrogen atom (2.145(3) Å), in good agreement with
the stronger trans effect of the phosphine with respect to the
amine. In both structures, Pd and Mn atoms are located at the
same side with respect to the η5-cyclohexadienyl plane. Carbonꢀ
carbon bond lengths within the allyl ligand are comparable with
other examples of η1-allyl complexes reported in the literature.31ꢀ34
2.4. Application in Catalysis. The efficiency of a selection of
mono- and bidentate ligands was evaluated in a representative
palladium-catalyzed allylic substitution using 1,3-diphenyl-3-acet-
oxy-1-propene as the substrate and dimethyl malonate as the
nucleophile under the classical conditions using BSA/KOAc as
the base in CH2Cl2 (Scheme 5). The following amounts of
the precursor [Pd(η3-allyl)Cl]2 were used: 0.25 equiv with the
monodentate ligands 5a and 6ꢀ8 and 0.5 equiv with the bidentate
ligands 15, 20, and 31.Typically, the catalytic experiments were
performed at three different temperatures and the progress of
the reaction was followed by 1H NMR. Experimental conditions
for total conversion are given in Table 5, where the structures of
the ligands were simplified for reasons of clarity.
Figure 5. ORTEP views of the neutral palladiꢀum complex 33 (top)
and the cationic complex 34 (bottom; the PF6 anion is omitted for
clarity), with thermal ellipsoids at the 30% probability level). Selected
bond lengths (Å): for 33, PdꢀN = 2.2780(19), PdꢀP = 2.2310(7),
C33ꢀC34 = 1.321(4), C32ꢀC33 = 1.462(4); for 34, PdꢀN = 2.187(2),
PdꢀP = 2.2988(7), PdꢀC32 = 2.145(3), PdꢀC33A = 2.180(4),
PdꢀC33B = 2.175(13), PdꢀC34 = 2.239(3), C32ꢀC33A = 1.357(5),
C32ꢀC33B = 1.245(15), C33AꢀC34 = 1.401(6), C33BꢀC34 = 1.341(16).
Scheme 5. Allylic Alkylation Tested with Ligands L Based on
η5 Mn Complexes
The reaction is extremely fast, with all the ligands tested
reaching total conversion with excellent yields in less than 15 min
at room temperature, which is a quite short reaction time
compared to that for other studies.11,12
Within the series of monodentate ligands 5a and 6ꢀ8 (Table 5,
entries 1ꢀ4), at 0 °C, the fastest reaction is obtained with the C2
phosphino-substituted ligand 7, as is the case at ꢀ40 °C. Indeed,
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Table 5. Catalytic Tests with Mono- and Bidentate Ligands
Based on η5 Mn Complexes (Total Conversion and Yield
>90%)
Table 6. 31P NMR Data (δ in ppm and J in Hz) for P(III) and
P(V) Derivatives in CDCl3
catalyst is increased, which could explain the very fast reaction
observed at 0 °C or room temperature with the corresponding
catalysts (Table 5). These data suggest first that the Mn(CO)3
tripod coordinated in an η5 manner to the cycle amplifies the
electronic effects of the substituents (here only electron donating)
(764ꢀ743 Hz is greater than 728.9ꢀ720 Hz) and second that
this metal coordination noticeably decreases the electron density
at the phosphorus atom.42 We can also conclude that the Lewis
acidity of the phosphorus atom decreases in the order 5a-Se >
7-Se > 6-Se > 8-Se > PPh3 > PPh2(2-OMe-C6H4). However, at
this stage, it is difficult to link the efficiency of the catalyst only
to the acidity of the phosphorus atom of the ligand, because the
electron density at phosphorus is not the only parameter gov-
erning the rate of the process and the steric hindrance of the
ligand probably plays a role.
2.4.1. Preparation of Enantioenriched Ligands. As the new
metalloligands were effective in catalysis, we next investigated their
preparation in enantiopure form in order to use them in enantio-
selective catalysis. Planar chiral ligands which only possess planar
chirality are relatively rare.5,11,12,43 Very few syntheses of en-
antioenriched η5 Mn complexes have been described in the
literature over the last 3 years. They involve either a resolution via
a chiral nonracemic auxiliary or an enantioselective synthesis starting
from enantiopure η6 Mn complexes, and these two methodologies
were applied in the present study to the synthesis of enantioen-
riched Mn-based ligands.
2.4.1.1. Resolution via a Chiral Nonracemic Palladium
Auxiliary. In the literature, enantioenriched η5 Mn complexes have
been obtained by resolution of a planar chiral formyl-substituted η5
complex through the formation of the corresponding aminal from a
chiral diamine.22a,c,44 We adopted an analogous method involving
an enantiopure palladium auxiliary which could coordinate the
PPh2 substituent of the racemic (η5-cyclohexadienyl)Mn(CO)3
complexes.
The dimeric palladium complex (S)-(þ)-bis(μ-chloro)bis[2-
[(dimethylamino)ethyl]phenyl-C2,N]dipalladium(II) ((S)-35) was
chosen as the chiral resolving agent.45 Following the protocol
previously described by Mino and co-workers,45c (()-6 was totally
converted to the diastereoisomeric palladium complex mixture 36,
which was purified on a silica gel chromatography column thanks
to a suitable degree of separation of the two diastereoisomers
(Scheme 6). (S,3pS)-36 and (S,3pR)-3623,46 were isolated in 40%
and 34% yields, respectively, with dr g 95:5. The diastereoiso-
meric purity of each fraction was unambiguously confirmed by
1H NMR analysis: the signal corresponding to the H4 proton of
each diastereoisomer, ortho to the chelating phosphine, resonates
a Conditions: [substrate] = 0.39 mol Lꢀ1, [nucleophile] = 1.16 mol Lꢀ1
,
[Pd(η3-allyl)Cl]2 = 0.01 mol Lꢀ1, [BSA] = 1.16 mol Lꢀ1 b Time in
minutes except when indicated. c Time in hours.
full conversion was reached within 10 min, as compared to hours
in all other cases (Table 5). The same observation can be made in
the case of both regioisomers 15 and 20 at ꢀ40 °C, where the C2-
substituted phosphorus ligand provides an almost 4 times faster
reaction than the C3-substituted ligand (entries 5 and 6), support-
ing the idea that the influence of the η5 system on the phosphorus
atom might depend on the position of this atom on the π system.38
It is suggested that the less basic the phosphorus atom, the faster
the reaction. This is consistent with the increase of electrophi-
licity of the palladium center favoring most probably the nucleo-
philic addition to the allylic moiety.
To find out more about the electronic density of the new
phosphorus ligands, we used the method of Allen and Taylor,39ꢀ41
who demonstrated that the 1JPꢀSe coupling constant was a good
measure of the phosphine basicity, irrespective of the size of
the phosphine. Thus, the PꢀSe complexes were readily prepared
from the mono- and disubstituted ligands applied in catalysis, 5a
and 6ꢀ8 (Table 5), in quantitative yields by heating a solution
of the ligand with an excess of selenium in chloroform for 5 h.
This procedure delivered the PꢀSe derivatives, which are the
first examples of such complexes ever described in the literature
(Table 6). Table 6 contains a summary of the NMR data for the
ligands investigated. The 764 Hz 1JSeꢀP coupling constant value of
complex 5a-Se is higher than those obtained for 6-Se and 8-Se at
743 and 741 Hz, in good agreement with the presence of an
electron-donating methoxy group “ortho” or “para” to the phos-
phorus atom (entries 1, 2, and 4). A milder effect is observed when
MeO is located at the “meta” position, with a J value of 756 Hz
(entry 3). More interesting is the comparison of the coupling
constants of 5a-Se and 6-Se, which have values of 764 and 743 Hz,
respectively (entries 1 and 2), with those of the aryl-substituted
phosphino ligands PPh3dSe and PPh2(2-OMe-C6H4) with
J values of 728.9 and 720 Hz, respectively (entries 5 and 6). This
underlines that when the phenyl group of the P atom is replaced
by the (η5-cyclohexadienyl)Mn(CO)3 ligand, a strong π-acceptor
effect is observed on the P atom and the Lewis acidity of the
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at 5.91 and 6.52 ppm, respectively. The configuration of the
planar chiral moiety was determined by single-crystal X-ray
analysis of the more polar palladium complex (δ(H4) 5.91 ppm),
which revealed the pS configuration for the phosphine complex
(S,3pS)-3623 on the basis of the S configuration of the enantio-
pure phenethylamine moiety. Each diastereoisomer was then
treated with ethylenediamine in order to release the enantiopure
complexes (3pS)-6 and (3pR)-6 in 77% and 84% yields, respec-
tively, and 90% ee.
Using the same procedure, we then carried out further in
vestigations to resolve 7 and 8. The reaction of the palladium
complex (S)-35 with 7 and 8 readily proceeded to deliver the
corresponding bimetallic derivatives 37 and 38 in 95 and 97%
yields, respectively, as a mixture of two diastereomers (Scheme 7).
Unfortunately, they could not be separated on a chromatography
column. In any event, to our surprise, by slow diffusion of pentane
in a dichloromethane solution of 38 mixture at low temperature
two kinds of shiny crystals, with two very distinct colors, yellow
and orange, appeared. They could be easily separated and isolated
in 32 and 34% yields and with 88 and 86% de, respectively, as
evidenced by 1H NMR spectra.
The assignment of the pS configuration of the planar chiral
moiety was determined by single-crystal X-ray analysis of one
of the yellow crystals (Figure 6 and Table 3).26 The C1C6C5/
C1C2C3C4C5 dihedral angle has a slightly smaller value than that
for 15, 33, and 34: 35.44(15)° in comparison with 41° (Table 3).
The palladium atom is located at the side opposite the Mn(CO)3
tripod. The structure shows a square-planar coordination of
the palladium, with the sum of all bond angles of 359.8°. Each
diastereoisomer of 38, after treatment with ethylenediamine, de-
livered the enantioenriched (1pS)-8 and (1pR)-8 in 88% yield
and with 88 and 86% ee, respectively.
2.4.1.2. Enantioselective Syntheses. The second procedure
used for the preparation of Mn-based ligands in enantioenric-
hed forms was based on enantioselective syntheses starting from
enantiopure η6 Mn complexes. In 2009, we published the first
method of resolution of cationic ortho- andmeta-disubstituted (η6-
arene)tricarbonylmanganese complexes based on D-(þ)-camphor
Scheme 6. Resolution of Complex 6
Figure 6. ORTEP view of yellow (S,1pS)-38, with thermal ellipsoids at
the 30% probability level. Selected bond lengths (Å): PdꢀN1
=
2.134(2), PdꢀP1 = 2.2611(7), PdꢀC29 = 2.003(2), PdꢀCl =
2.4099(7).
Scheme 7. Resolution of Complexes 7 and 8
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Scheme 8. Enantioselective Synthesis of Bidentate PꢀN
Table 7. Enantioselective Catalysis Tests at 20 °C with
Ligand 15
Mono- and Bidentate Ligands Based on η5 Mn Complexes
(Total Conversion and Yield >90%)a
entry
1
2
3
4
5
6
ligand
timeb
eec
(ꢀ)-6
7
(þ)-6
7
(ꢀ)-8
15
(þ)-8
15
(þ)-15
5
(ꢀ)-15
5
35 (R)
43 (S)
6 (R)
3 (S)
83 (S)
79 (R)
a Conditions: [substrate] = 0.39 mol Lꢀ1, [nucleophile] = 1.16 mol Lꢀ1
,
[Pd(η3-allyl)Cl]2 = 0.01 mol Lꢀ1, [BSA] = 1.16 mol Lꢀ1. b Time in min.
c In percent; determined by HPLC using a chiral Chiralpak AD-H
column. Separation conditions: hexane/iPrOH 9/1, trR = 11.2 min,
trS = 15.4 min.
Typically, the catalytic tests were performed at 20 °C, and the
results (followed by 1H NMR spectroscopy, total conversion and
yield >90%) are gathered in Table 7. Fair ee’s were obtained with
ligands 6 (entries 1 and 2), and very low ee’s are observed with
ligands 8 (entries 3 and 4); however, much better ee’s are achieved
with (N,P) ligands 15, which performed more efficiently in this
reaction. Thus, after 5 min the substitution products were formed
in excellent yields with ee’s of 83 and 79% (entries 5 and 6). The
use of lower temperatures did not give higher levels of induction.
These results suggest a correlation between the coordination
ability of the ligand and the selectivity of the corresponding
catalysts. Indeed, the lowest selectivity is obtained with the mono-
phosphine 8. Ligand 6, which possesses a methoxy group close to
the phosphorus moiety, provides a catalyst showing moderate
selectivity. The assistance of the methoxy group, through either
steric hindrance or chelation, can be reasonably thought to support
the observed variation of selectivity. Finally, the catalyst bearing the
P,N bidentate ligand 15 exhibits the highest selectivity.
Figure 7. Enantioenriched mono- and bidentate ligands synthesized in
the present study.
enolate addition, separation of the corresponding η5-cyclohex-
adienyl diastereoisomers, and then elimination of the chiral
auxiliary by rearomatization.20,47 The addition of PhMgBr to the
enantiomer 1pS of the cationic tricarbonylmanganese m-bro-
moanisole complex prepared according to this procedure20 deliv-
ered the corresponding enantiopure η5 complex (2pS)-3 with the
same planar chirality, as it is well precedented that the nucleophile
usually attacks exo to the Mn(CO)3 entity (Scheme 8). Halogenꢀ
metal exchange followed by treatment with methanol gave the
enantiopure (2pS)-2, a key organometallic chiral synthon that
cannot be obtained through resolution of the (η6-anisole)Mn-
(CO)3 parent complex, because this latter monosubstituted com-
plex has no planar chirality. The following steps are the same as
in the racemic series, and two consecutive lithiationꢀelectrophilic
quenches with the Eschenmoser salt and then with PPh2Cl as
electrophile delivered the enantiopure (2pR)-15 from (2pS)-10.
As neither lithiation nor electrophilic quenching involves planar
chirality, we assumed that this methodology does not modify the
stereochemical information and compounds (2pS)-3, (2pS)-2,
(2pS)-10, and (2pR)-15 were obtained in >98% ee. With the
cationic 1pR enantiomer as the starting material, the same protocol
led to (2pS)-15.
3. CONCLUSION
We have reported the synthesis of phosphino-substituted (η5-
cyclohexadienyl)Mn(CO)3, potential mono- and bidentate ligands,
in good to excellent yields by functionalization of the η5 scaffold
using lithiationꢀelectrophilic quenching sequences and palladium-
catalyzed coupling reactions. The coordination properties of one
monodentate and one bidentate P,N η5 ligand were studied, and
the corresponding bimetallic Mn/Pd complexes were isolated and
structurally characterized by X-ray crystallography. The resolution
of three of them, involving two different approaches by using either
a chiral nonracemic palladium auxiliary or an enantioselective
synthesis, allowed us to isolate the first examples of enantioen-
riched ligands based on a η5 Mn unit.
The catalytic efficiency of a selection of ligands was evaluated
in a model reaction (the palladium-catalyzed allylic substitution)
which was revealed to be extremely fast and which occurred with
excellent yields and total conversion in all the examples studied.
The first results obtained in asymmetric catalysis, although not
optimized, are satisfying and open a new area for the application
of such η5 Mn complexes in this field.
4. EXPERIMENTAL SECTION
2.4.2. Asymmetric Catalysis. The potential of the enantiopure
ligands 6, 8, and 15 (Figure 7) in asymmetric catalysis was then
surveyed and tested in the allylic alkylation represented in
Scheme 5.
4.1. General Procedures. All reactions were routinely performed
under a dry nitrogen atmosphere using standard Schlenk techniques.
THF was dried over sodium benzophenone ketyl and distilled. N,N,N0,
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N0-Tetramethylethylenediamine (TMEDA) was distilled over KOH and
stored under nitrogen over 4 Å molecular sieves. Acetone and benzal-
dehyde were distilled over K2CO3. NMR spectra were recorded on a
Bruker ARX 200 MHz or Avance 400 MHz spectrometer. Infrared spectra
were measured on a Bruker Tensor 27 spectrometer. Elemental analyses
were performed by the Service Central d’Analyse du CNRS. Mass spectra
were performed for MALDI-TOF by the Plate-Forme Spectromꢀetrie
de Masse and Protꢀeomique (IFR83, UPMC), for ES-MS by the Groupe
de Spectromꢀetrie de Masse (UMR 7613, UPMC), and for EI-MS by the
Service de Spectromꢀetrie de Masse de l’ENS (Chemistry Department,
Paris).
Data for 5a (30% yield) are as follows. 1H NMR (400 MHz, CDCl3):
δ 3.44 (t, 3J = 6.3 Hz, 1H, H5), 3.60 (t, 3J = 6.3 Hz, 1H, H6), 3.98 (t, 3J =
6.3 Hz, 1H, H1), 5.14 (t, 3J = 6.3 Hz, 1H, H4), 5.30 (d, 3J = 2.9 Hz, 1H,
H3), 6.92 (m, 4H, HAr), 7.02 (t, 3J = 6.9 Hz, 2H, HAr), 7.30 (m, 9H, HAr)
ppm. 13C NMR (100 MHz, CDCl3): δ 40.6 (d, 3JCP = 4 Hz, C6), 56.5
(C5), 60.4 (d, 2JCP = 26 Hz, C1), 82.5 (d, 2JCP = 6 Hz, C3), 96.7 (C4),
1
111.1 (d, JCP = 17 Hz, C2), 125.9 (CHAr), 126.9 (CHAr), 128.6 (d,
3JCP = 7 Hz, CHAr), 128.8 (CHAr), 128.9 (d, 3JCP = 7 Hz, CHAr), 129.0
(CHAr), 130.2 (CHAr), 134.0 (d, 2JCP = 20 Hz, CHAr), 134.8 (d, 1JCP
=
12 Hz, CAr), 222.7 (Mn(CO)3) ppm. 31P NMR (162 MHz, CDCl3):
δ ꢀ2.7 (PPh2) ppm. IR (ATR Diamant): ν 1910 (Mn(CO)3), 2010
(Mn(CO)3) cmꢀ1. HRMS (ESI, positive mode): m/z 479.0616 (M þ
Hþ), calcd for C27H21MnO3P 479.0609. Anal. Calcd: C, 67.79; H, 4.21.
Found: C, 67.65; H, 4.12.
Complexes 1,48 2,48 3,19 4,19 21,18b 22,22c 23,22b and 2422b were
synthesized according to procedures previously described in the
literature.
Data for 5b (13% yield) are as follows. 1H NMR (400 MHz, CDCl3):
δ 3.50 (m, 2H, H1 and H5), 3.82 (t, 3J = 6.0 Hz, 1H, H6), 4.79 (m, 2H, H2
and H4), 6.85 (m, 3H, HAr), 6.93 (m, 2H, HAr), 7.18 (m, 8H, HAr), 7.35
(t, 3J = 7.0 Hz, 2H, HAr) ppm. 13C NMR (100 MHz, CDCl3): δ 38.5
(C6), 59.4 (d, 3JCP = 2.0 Hz, C1 and C5), 91.3 (C3), 100.9 (d, 2JCP = 18.1
Hz, C2 and C4), 125.5 (CHAr), 126.7 (CHAr), 128.4 (CHAr), 128.5
(CHAr), 128.6 (CHAr), 129.1 (CHAr), 133.8 (d, 2JCP = 19.5 Hz, CHAr),
136.4 (d, 1JCP = 9.7 Hz, CAr), 143.8 (C7) ppm. 31P NMR (162 MHz,
CDCl3): δ ꢀ3.6 (PPh2) ppm. IR (ATR Diamant): ν 1927 (Mn(CO)3),
4.2. Typical Procedure for LithiationꢀElectrophilic Quench-
ing Sequence: Method A. A solution of (η5-cyclohexadienyl)Mn-
(CO)3 (0.5 mmol) and freshly distilled TMEDA (0ꢀ2 equiv; see
Table 1) in 5 mL of THF was cooled to ꢀ78 °C. A solution of n-BuLi
(1.6 M in hexanes; 1.4ꢀ2 equiv; see Table 1) was slowly added. The
mixture was stirred for 15 min to 2 h (see Table 1) at ꢀ78 °C before the
addition of the electrophile (1.6ꢀ2.5 equiv; see Table 1). The mixture
was stirred for another 1 h at ꢀ78 °C before it was warmed to room
temperature and quenched by addition of H2O. After extraction of the
mixture by Et2O, the combined organic layers were washed with a
saturated aqueous NaCl solution and dried over MgSO4. After filtration
and concentration in vacuo, the crude mixture was purified by flash
chromatography on silica gel to afford the pure functionalized η5-cy-
clohexadienyl complex.
4.3. Typical Procedure for MetalꢀHalogen Exchange and
Then Electrophilic Quenching: Method B. n-BuLi (3 equiv) was
dropped into a THF solution cooled to ꢀ78 °C. Then a solution of the
η5 bromo-substituted complex (1 equiv) in THF was very slowly added,
giving rise to a deep yellow-orange solution that was stirred at ꢀ78 °C
for 10 min. The electrophile (3.5 equiv) was added, and the solution was
very slowly warmed to room temperature. The crude mixture was
hydrolyzed with water, and the aqueous layer was extracted with diethyl
ether. The organic layers were washed with water and then brine and
dried over MgSO4. After filtration over Clarcel and evaporation of the
solvents, the mixture was purified by flash chromatography on silica gel.
4.4. Typical Procedure for Palladium-Catalyzed Coupling:
Method C. Pd2(dba)3 (0.03 mmol) and AsPh3 (0.11 mmol) were
successively added to the η5 complex (0.32 mmol) in 7 mL of anhydrous
degassed DMF. After 5 min at room temperature tributylstannylthio-
phene (0.32 mmol) was introduced. The mixture was stirred for 23 h
at room temperature, poured into 50 mL of ice-cold water, and extracted
twice with 30 mL of pentane. The combined organic phases were washed
with H2O (20 mL) and dried over MgSO4. After filtration and concen-
tration in vacuo, the crude mixture was purified by flash chromatogra-
phy on silica gel to afford the pure functionalized η5-cyclohexadienyl
complex.
2021 (Mn(CO)3) cmꢀ1
.
Data for 6 (83% yield; method A) are as follows. 1H NMR (400 MHz,
CDCl3): δ 3.35 (m, 1H, H5), 3.43 (s, 3H, OMe), 3.56 (m, 1H, H1), 4.02
(t, 3J = 6.0 Hz, 1H, H6), 4.39 (d, 3J = 7.4 Hz, 1H, H4), 6.98 (d, 3J = 7.0 Hz,
2H, HAr), 7.22ꢀ7.37 (m, 9H, HAr), 7.44ꢀ7.47 (m, 4H, HAr) ppm. 13
C
NMR (100 MHz, CDCl3): δ 41.6 (C6), 42.3 (C1), 55.1 (OMe), 57.7
1
(C5), 81.2 (d, JCP = 20 Hz, C3), 95.7 (C4), 125.5 (CHAr), 127.0
(CHAr), 128.6 (d, 3JCP = 7 Hz, CHAr), 128.8 (CHAr), 128.9 (d, 3JCP
=
2
7 Hz, CHAr), 128.9 (CHAr), 129.8 (CHAr), 133.4 (d, JCP = 20 Hz,
1
2
CHAr), 135.0 (d, JCP = 12 Hz, CAr), 135.1 (d, JCP = 20 Hz, CHAr),
137.6 (d, 1JCP = 12 Hz, CAr), 146.2 (d, 2JCP = 14 Hz, C2), 147.7 (CAr)
ppm. 31P NMR (162 MHz, CDCl3): δ ꢀ17.2 (PPh2) ppm. IR (ATR
Diamant): ν 1917 (Mn(CO)3), 2009 (Mn(CO)3) cmꢀ1. HRMS (ESI,
positive mode): m/z 509.0266 (M þ Hþ), calcd for C28H23MnO4P
509.0714. Anal. Calcd for C28H23MnO4P: C, 66.15; H, 4.36. Found:
C, 66.06; H, 4.07.
Data for 7 (96% yield; method B) are as follows. 1H NMR (200 MHz,
CDCl3): δ 3,37 (d, 3J = 5.9 Hz, 1H, H5), 3.46 (d, 3J = 5.9 Hz, 1H, H1),
3
3.54 (s, 3H, OMe), 4.10 (t, J = 5.9 Hz, 1H, H6), 5.35 (s, 1H, H3),
6.86ꢀ6.90 (m, 2H, HAr), 7.00ꢀ7.09 (m, 4H, HAr), 7.19ꢀ7.49 (m, 9H,
HAr) ppm. 13C NMR (400 MHz, CDCl3): δ 41.3 (C5), 43.0 (d, JCP = 4
Hz, C6), 54.6 (OMe), 60.4 (d, 1JCP = 26 Hz, C1), 71.3 (d, JCP = 8 Hz,
C3), 107.2 (d, JCP = 17 Hz, C2), 125.7 (CHAr), 126.8 (CHAr), 128.6
(CHAr), 128.7 (CHAr), 128.8 (CHAr), 128.9 (CHAr), 129.0 (CHAr),
129.9 (CHAr), 133.0 (d, JCP = 18 Hz, CHAr), 133.9 (d, JCP = 20 Hz,
CHAr), 135.1 (d, JCP = 20 Hz, CHAr), 143.3 (C4), 146.6 (CAr), 222.4
(Mn(CO)3) ppm. 31P NMR (162 MHz, CDCl3): δ ꢀ2.0 (PPh2) ppm.
IR (ATR Diamant): ν 1902 (Mn(CO)3), 2013 (Mn(CO)3) cmꢀ1
.
4.5. Typical Procedure for Catalysis. In a Schlenk tube were
introduced [Pd(η3-allyl)Cl]2 (0.03 equiv) and the monodentate ligand
(0.12 equiv.) in 1 mL of CH2Cl2, and the mixture was stirred for 30 min.
In a second tube, KOAc (0.1 equiv), BSA (3 equiv) (KOAc and BSA
generate in situ the nucleophile in order to keep the concentration of
nucleophile constant with respect to the catalyst during the reaction)
and dimethyl malonate (3 equiv) were introduced with 1 mL of CH2Cl2;
the mixture was stirred for 30 min and added to the first Schlenk tube
together with a solution of allyl acetate (1 equiv) in 1 mL of CH2Cl2. The
time and reaction temperature are detailed in Tables 5 and 6.
5a,b (method A) could not be separated by a chromatography
column, but the difference in their solubilities in pentane allowed us
to isolate pure 5a (partially soluble in pentane) and a mixture of 5a
and 5b.
HRMS (ESI, positive mode): m/z 509.0709 (M þ Hþ), calcd for
C28H23MnO4P 509.0714.
Data for 8 (67% yield; method B) are as follows. 1H NMR (200 MHz,
CDCl3): δ 3,27 (dd, 3J = Hz, 4J = Hz, 1H, H5), 3.50 (s, 3H, OMe), 4.13
(t, 3J = Hz, 1H, H6), 4.87 (t, 3J = Hz, 1H, H2), 5.79 (dd, 3J = Hz, 4J = Hz,
1H, H3), 6.80ꢀ6.82 (m, 2H, HAr), 6.95ꢀ7.26 (m, 13H, HAr) ppm. 13
C
NMR (400 MHz, CDCl3): δ 41.7 (d, 3JCP = 9 Hz, C5), 48.4 (d, 2JCP = 24
Hz, C6), 54.8 (OMe), 68.6 (C3), 70.6 (d, 1JCP = 30 Hz, C1), 97.1 (d, 2JCP
= 4 Hz, C2), 126.9 (CHAr), 127.5 (CHAr), 128.0 (d, 2JCP = 7 Hz, CHAr),
128.3 (CHAr), 128.5 (CHAr), 128.6 (CHAr), 129.7 (CHAr), 133.7 (d,
2JCP = 20 Hz, CHAr), 135.0 (d, 2JCP = 20 Hz, CHAr), 135.5 (d, 1JCP = 12
Hz, CAr), 135.7 (d, 1JCP = 11 Hz, CAr), 143.1 (C4 or C7), 146.5 (C4 or
C7) ppm. 31P NMR (162 MHz, CDCl3): δ 4.4 (PPh2) ppm. IR (ATR
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Diamant): ν 1929 (Mn(CO)3), 2021 (Mn(CO)3) cmꢀ1. HRMS (ESI,
positive mode): m/z 509.0709 (M þ Hþ), calcd for C28H23MnO4P
509.0714.
(d, 2JCP = 5 Hz, C5), 91.3 (d, JCP = 21 Hz, C3 or C4), 109.5 (d, JCP = 23 Hz,
C3 or C4), 125.6 (CHAr), 127.0 (CHAr), 127.7 (d, 3JCP = 8 Hz, CHAr),
3
127.9 (CHAr), 128.6 (d, JCP = 12 Hz, CHAr), 129.0 (CHAr), 129.5
1
2
2
Data for 923 (70% yield; method A) are as follows. H NMR (400
(CHAr), 132.9 (d, JCP = 16 Hz, CHAr), 134.8 (CAr), 136.1 (d, JCP
=
MHz, CDCl3): δ 3.14 (s, 3H, OMe), 3.42 (tapp, 3J = 6.0 Hz, 1H, H1),
3.63 (tapp, 3J = 6.0 Hz, 1H, H5), 4.02 (t, 3J = 6.0 Hz, 1H, H6), 5.74 (t, 3J =
7.0 Hz, 1H, H4), 6.97 (d, 3J = 7.0 Hz, 2H, H8), 7.22ꢀ7.29 (m, 5H, HAr),
7.42ꢀ7.56 (m, 4H, HAr), 7.75ꢀ7.89 (m, 4H, HAr) ppm. 13C NMR (100
MHz, CDCl3): δ 41.5 (C6), 42.7 (C1), 54.3 (OMe), 60.3 (C5), 97.3
(C4), 125.5 (CHAr), 127.2 (CHAr), 127.9 (d, 2JCP = 12 Hz, CHAr), 128.6
20 Hz, CAr), 143.6 (d, 3JCP = 5 Hz, C2), 147.1 (CAr), 222.4 (Mn(CO)3)
ppm. 31P NMR (161 MHz, CDCl3): δ ꢀ9.2 (PPh2). IR (neat): ν 1925
(Mn(CO)3), 2010 (Mn(CO)3) cmꢀ1. HRMS (ESI, positive mode): m/z
566.1287 (M þ Hþ), calcd for C31H30O4MnNP 566.1293.
1
Data for 16 (71% yield; method A) are as follows. H NMR (200
MHz, CDCl3): δ 2.55 (s, 6H, NMe2), 3.28 (d, J = 5.6 Hz, 1H, H5),
3
(d, 2JCP = 12 Hz, CHAr), 128.7 (CHAr), 131.9 (CHAr), 132.1 (d, 3JCP
=
P
3.46 (d, 3J = 5.6 Hz, 1H, H1), 3.57 (s, 3H, OMe), 3.92 (m, 1H, H6), 3.98
(d, 2J = 12.8 Hz, 1H, H11), 4.17 (d, 2J = 12.8 Hz, 1H, H11), 7.13 (m, 10H,
HAr) ppm. 13C NMR (100 MHz, CDCl3): δ 41.4 (C5), 42.7 (C6), 45.7
(NMe2), 55.2 (OMe), 55.4 (C11), 57.5 (C1), 85.6 (C3), 115.8 (C4),
125.6 (CHAr), 126.9 (CHAr), 128.4 (CHAr), 128.7 (CHAr), 129.5 (CHAr),
133.3 (CAr), 133.5 (CHAr), 141.2 (CAr), 146.6 (C2), 222.1 (Mn(CO)3)
10 Hz, CHAr), 132.8 (CHAr), 147.2 (C2), 216.6 (Mn(CO)3) ppm. 31
NMR (CDCl3): δ 30.3 ppm. IR (neat): ν 1952 (Mn(CO)3), 2015-
(Mn(CO)3) cmꢀ1. HRMS (ESI, positive mode): m/z 525.0658 (M þ
Hþ), calcd for C28H23O5MnP 525.0664.
Data for 1023 (77% yield; method A) are as follows. 1H NMR (400
MHz, CDCl3): δ 2.41 (s, 6H, NMe2), 3.06 (d, 2J = 12.5 Hz, 1H, H11),
3.31 (ddd, 3J = 7.3 Hz, 3J = 6.2 Hz, 4J = 1.6 Hz, 1H, H5), 3.40 (dd, 3J = 6.2
Hz, 4J = 1.6 Hz, 1H, H1), 3.42 (s, 3H, OMe), 3.91 (tapp, 3J = 6.2 Hz, 1H,
H6), 4.21 (d, 2J = 12.5 Hz, 1H, H11), 5.05 (d, 3J = 7.3 Hz, 1H, H4), 6.94
(d, 3J = 7.3 Hz, 2H, HAr), 7.13 (t, 3J = 7.3 Hz, 1H, HAr), 7.21 (tapp, 3J = 7.3
Hz, 2H, HAr) ppm. 13C NMR (100 MHz, CDCl3): δ 41.5 (C1), 42.6
(C6), 45.5 (NMe2), 54.8 (OMe), 56.2 (C5), 59.0 (C11), 85.3 (C3), 97.2
(C4), 125.6 (CHAr), 127.0 (CHAr), 128.8 (CHAr), 143.4 (C2 or CAr),
147.5 (C2 or CAr), 222.9 (Mn(CO)3) ppm. IR (neat): ν 1909
(Mn(CO)3), 2006 (Mn(CO)3) cmꢀ1. HRMS (MALDI TOF, positive
mode): m/z 382.0798 (M þ Hþ), calcd for C19H21O4MnN 382.0851.
ppm. IR (ATR Diamant): ν 1919 (Mn(CO)3), 2009 (Mn(CO)3) cmꢀ1
.
HRMS (ESI, positive mode): m/z 490.0879 (M þ Hþ), calcd for
C25H25MnNO4S 490.0885.
Data for 17 (obtained by NaBH4 reduction of the corresponding
aldehyde: 80% yield (method A)) are as follows. 1H NMR (400 MHz,
CDCl3): δ 2.33 (s, 6H, NMe2), 3.36 (m, 4H, OMe and H5), 3.55 (m,
2H, H1 and H11), 3.79 (d, 2J = 13.1 Hz, 1H, H12), 3.94 (m, 2H, H6 and
H12), 4.71 (d, 2J = 10.3 Hz, 1H, H11), 7.07 (m, 2H, HAr), 7.22 (m, 3H,
HAr) ppm. 13C NMR (100 MHz, CDCl3): δ 41.5 (C6), 42.4 (C1), 44.5
(NMe2), 54.0 (C12), 55.1 (OMe), 58.2 (C5), 66.6 (C11), 85.3 (C4),
111.2 (C3), 125.4 (CHAr), 126.8 (CHAr), 128.8 (CHAr), 141.2 (C2 or
C7), 147.8 (C2 or C7) ppm. IR (ATR Diamant): ν 1915 (Mn(CO)3),
2028 (Mn(CO)3) cmꢀ1. HRMS (ESI, positive mode): m/z 412.0956
(M þ Hþ), calcd for C20H23MnNO5 412.0957.
1
Data for 11 (37% yield; method A) are as follows. H NMR (400
MHz, CDCl3): δ 2.81 (s, 3H, OMe), 3.50 (d, 3J = 5.9 Hz, 1H, H1), 3.88
(t, 3J = 5.9 Hz, 1H, H6), 4.31 (d, 3J = 5.9 Hz, 1H, H5), 6.98 (d, 3J = 7.0 Hz,
1
1H, HAr), 7.30ꢀ7.57 (m, 9H, HAr), 7.70ꢀ7.80 (m, 4H, HAr) ppm. 13
C
Data for 18 (51% yield; method A) are as follows. H NMR (200
NMR (100 MHz, CDCl3): δ 43.8 (C1), 44.0 (C6), 54.3 (OMe), 72.4
MHz, CDCl3): δ 2.10 (s, 6H, NMe2), 2.40 (s, 6H, NMe2), 2.68 (d,
2J = 13.6 Hz, 1H, H11 or H12), 3.37 (m, 2H, H11), 3.44 (s, 3H, OMe),
3.63 (m, 2H, H11 and H13), 3.92 (m, 2H, H11 or H13 and H6), 6.94 (d,
3J = 6.5 Hz, 1H, HAr), 7.12 (m, 3H, HAr) ppm. 13C NMR (100 MHz,
CDCl3): δ 41.3 (C1), 42.4 (C6), 45.8 (NMe2), 46.2 (NMe2), 54.1 (C11
or C13), 54.9 (OMe), 61.2 (C11 or C13), 86.6 (C3), 110.4 (C4), 125.8
(CHAr), 126.9 (CHAr), 128.7 (CHAr), 141.9 (C2 or CAr), 147.3 (C2 or
CAr), 222.9 (Mn(CO)3) ppm. IR (ATR Diamant): ν 1916 (Mn(CO)3),
2005 (Mn(CO)3) cmꢀ1. HRMS (ESI, positive mode): m/z 439.1424
(M þ Hþ), calcd for C22H28MnN2O4 439.1430.
(C5), 76.8 (C3), 125.4ꢀ134.4 (CHAr), 146.6 (C2), 149.4 (C4) ppm. 31
P
NMR (162 MHz, CDCl3): δ 35.0 (P(O)Ph2) ppm. IR (ATR Diamant):
ν 1935 (Mn(CO)3), 2014 (Mn(CO)3) cmꢀ1. Anal. Calcd: C, 51.72; H,
3.26. Found: C, 51.36; H, 3.19.
1
Data for 13 (95% yield; method A) are as follows. H NMR (200
MHz, CDCl3): δ 0.32 (s, 1H, SiMe3), 2.27 (s, 6H, NMe2), 3.38 (d, 3J =
5.3 Hz, 1H, H5), 3.47 (s, 3H, OMe), 3.59 (d, 3J = 4.9 Hz, 1H, H1), 3.67
(s, 2H, H11), 3.95 (m, 1H, H6), 7.10 (m, 5H, HAr) ppm. 13C NMR (100
MHz, CDCl3): δ 0.4 (SiMe3), 41.9 (C1 or C6), 44.8 (NMe2), 54.7
(OMe), 54.9 (C11), 59.1 (C5), 91.3 (C3 or C4), 125.5 (CHAr), 126.5
(CHAr), 128.5 (CHAr), 143.0 (C2 or CAr), 148.3 (C2 or CAr), 222.9
(Mn(CO)3) ppm. IR (ATR Diamant): ν 1891 (Mn(CO)3), 1996
(Mn(CO)3) cmꢀ1. HRMS (ESI, positive mode): m/z 454.1241 (M þ
Hþ), calcd for C22H29MnNO4Si 454.1246.
1
Data for 19 (57% yield; method B) are as follows. H NMR (200
MHz, CDCl3): δ 2.15 (s, 6H, NMe2), 2.50 (d, 2J = 10.3 Hz, 1H, H11),
3.05 (d, 2J = 10.3 Hz, 1H, H11), 3.37 (d, 3J = 5.8 Hz, 1H, H1), 3.45 (d, 3J =
5.8 Hz, 1H, H5), 3.57 (s, 3H, OMe), 3.97 (t, 3J = 5.8 Hz, 1H, H6), 5.75 (s,
1H, H3), 6.95 (d, 3J = 7.3 Hz, 2H, HAr), 7.13 (d, 3J = 7.3 Hz, 1H, HAr),
7.21 (t, 3J = 7.3 Hz, 2H, HAr) ppm. 13C NMR (400 MHz, CDCl3): δ 43.4
(C1 and C6), 45.5 (NMe2), 54.7 (OMe), 61.5 (C5), 65.6 (C7), 70.4 (C3),
106.8 (C4), 125.8 (CHAr), 127.0 (CHAr), 128.7 (CHAr), 142.5 (C2 or C8),
147.4 (C2 or C8), 222.8 (Mn(CO)3) ppm. IR (ATR Diamant): ν 1908
(Mn(CO)3), 2005 (Mn(CO)3) cmꢀ1. HRMS (ESI, positive mode): m/z
382,0849 (M þ Hþ), calcd for C19H21MnNO4 382,0851.
Data for 1423 (94% yield; method A) are as follows. 1H NMR (400
MHz, CDCl3): δ 2.44 (s, 6H, NMe2), 3.39 (s, 3H, OMe), 3.49 (d, 3J =
6.1 Hz, 1H, H1), 3.59 (d, 2J = 12.8 Hz, 1H, H11), 3.84 (m, 2H, H5 and
H6), 4.14 (d, 2J = 12.8 Hz, 1H, H11), 6.92 (d, 3J = 7.5 Hz, 2H, HAr), 7.15
(t, 3J = 7.3 Hz, 1H, HAr), 7.23 (t, 3J = 7.7 Hz, 2H, HAr). 13C NMR (100
MHz, CDCl3): δ 43.8 (C1), 45.5 (C6), 45.6 (NMe2), 55.3 (OMe), 60.7
(C11), 65.6 (C5), 78.9 (C3 or C4), 88.5 (C3 or C4), 125.6 (CHAr), 127.3
(CHAr), 128.9 (CHAr), 139.2 (CAr), 146.9 (C2). IR (neat): 1910
(Mn(CO)3), 2022 (Mn(CO)3) cmꢀ1. HRMS (ESI, positive mode):
m/z 507.9812 (M þ Hþ), calcd for C19H20IMnNO4 507.9818.
1
Data for 20 (51% yield; method A) are as follows. H NMR (400
MHz, CDCl3): δ 2.08 (s, 6H, NMe2), 2.39 (dd, 4J = 6.1 Hz, 2J = 12.5 Hz,
1H, H11), 3.02 (s, 3H, OMe), 3.29 (d, 3J = 5.9 Hz, 1H, H1), 3.79 (m, 1H,
H5), 4.02 (t, 3J = 5.9 Hz, 1H, H6), 4.31 (dd, 2J = 12.7 Hz, 4J = 5.1 Hz, 1H,
1
Data for 15 (84% yield; method A) are as follows. H NMR (400
H11), 7.02 (m, 2H, HAr), 7.23 (m, 8H, HAr), 7.69 (d, 5H, HAr) ppm. 13
C
MHz, CDCl3): δ 1.92 (s, 6H, NMe2), 3.19 (d, 3J = 6.1 Hz, 1H, H5), 3.28
(dd, 3J = 5.0 Hz, 4J = 1.3 Hz, 1H, H1), 3.61 (s, 3H, OMe), 3.83 (d, 2J = 12.7
Hz, 1H, H11), 3.97 (t, 3J = 6.0 Hz, 1H, H6), 4.14 (dd, 2J = 12.7 Hz, J = 4.1
Hz, 1H, H11), 6.81 (t, 3J = 7.6 Hz, 2H, HAr), 6.89 (t, 3J = 7.1 Hz, 2H, HAr),
6.95(d, 3J=7.2Hz, 2H,HAr), 7.10(t,3J=7.1Hz, 1H, HAr), 7.20ꢀ7.37 (m,
8H, HAr) ppm. 13C NMR (100 MHz, CDCl3): δ 37.7 (C1), 42.4
NMR (100 MHz, CDCl3): δ 41.1 (C1), 41.8 (C6), 45.3 (NMe2), 53.8
(OMe), 64.1 (C11), 64.2 (d, 3JCP = 5 Hz, C5), 88.3 (d, JCP = 36 Hz, C3),
3
125.8 (CHAr), 127.1 (CHAr), 127.6 (CHAr), 127.7 (d, JCP = 5 Hz,
CHAr), 128.8 (d, 3JCP = 5 Hz, CHAr), 128.6 (CHAr), 128.7 (CHAr), 132.5
(d, 2JCP =23Hz, CHAr), 135.6 (d, 2JCP =23Hz, CHAr), 139.7 (d, 2JCP = 12
Hz, C2 or C4), 144.9 (d, 2JCP = 4 Hz, C2 or C4), 147.5 (CAr) ppm. 31
P NMR (162 MHz, CDCl3): δ ꢀ12.3 (PPh2) ppm. IR (ATR Diamant):
3
(C6), 43.9 (NMe2), 54.6 (d, JCP = 13.7 Hz, C11), 55.0 (OMe), 61.5
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ν 1903 (Mn(CO)3), 2013 (Mn(CO)3) cmꢀ1. HRMS (ESI, positive
mode): m/z 566.1287 (M þ Hþ), calcd for C31H30MnNO4P 566.1293.
6.97 (m, 4H, HAr), 6.99 (m, 2H, HAr), 7.08 (m, 3H, HAr), 7.25 (m, 2H,
HAr), 7.48 (m, 5H, HAr) ppm. 13C NMR (100 MHz, CDCl3): δ 43.4
1
2
Data for 25 (44% yield; method A) are as follows. H NMR (200
(C5), 51.5 (C6), 54.7 (OMe), 70.3 (C3), 71.7 (d, JCP = 24 Hz, C1),
MHz, CDCl3): δ 2.29 (s, 6H, NMe2), 2.99 (d, 2J = 13.1 Hz, 1H, H13),
3.35 (d, 2J = 13.1 Hz, 1H, H13), 3.54 (s, 3H, OMe), 3.58 (d, 3J = 3.9 Hz,
1H, H5), 4.35 (d, 3J = 6.2 Hz, 1H, H6), 5.73 (s, 1H, H3), 7.05ꢀ7.07 (m,
2H, HAr), 7.20ꢀ7.27 (m, 3H, HAr) ppm. 13C NMR (100 MHz, CDCl3):
δ 45.1 (C5), 45.8 (NMe2), 53.7 (C6), 55.1 (OMe), 62.0 (C13), 68.0
(C3), 81.1 (C1), 104.6 (C2), 126.4 (CHAr), 127.8 (CHAr), 128.7
(CHAr), 141.3 (C4 or C7), 143.9 (C4 or C7), 221.7 (Mn(CO)3) ppm.
110.8 (d, 1JCP = 40 Hz, C2), 125.8 (CHAr), 126.7 (CHAr), 127.8 (CHAr),
127.9 (CHAr), 128.3 (d, 2JCP = 8 Hz, CHAr), 128.4 (CHAr), 129.0 (d,
2JCP = 7 Hz, CHAr), 129.2 (CHAr), 130.1 (d, 3JCP = 3 Hz, CHAr), 134.3
(d, 2JCP = 21 Hz, CHAr), 134.7 (CAr), 135.6 (d, 2JCP = 20 Hz, CHAr),
136.5 (d, 1JCP = 8 Hz, CAr), 141.8 (CAr), 142.1 (d, 1JCP = 5 Hz, CAr),
144.8 (CAr) ppm. 31P NMR (162 MHz, CDCl3): δ ꢀ6.5 (PPh2) ppm. IR
(ATR Diamant): ν 1925 (Mn(CO)3), 2010 (Mn(CO)3) cmꢀ1. HRMS
(ESI, positive mode): m/z 591.0586 (M þ Hþ), calcd for C32H25-
O4MnPS 591.0585.
IR (ATR Diamant): ν 1926 (Mn(CO)3), 2021 (Mn(CO)3) cmꢀ1
.
HRMS (ESI, positive mode): m/z 416.0456 (M þ Hþ), calcd for
4.6. Synthesis of 32.23 The dimeric complex [(allyl)PdCl]2
(0.068 g, 0.20 mmol, 1 equiv) was introduced in a Schlenk tube. Then,
under N2, complex 6(0.213 g, 0.42 mmol, 2.1 equiv) was added. At ꢀ78 °C,
Et2O (5 mL) was added and the mixture was stirred for 30 min at ꢀ78 °C
before it was slowly warmed to room temperature. After concentration in
vacuo, the crude mixture was washed with pentane and filtered. The
palladium complex 32 was isolated in 63% yield as a cream-colored powder.
Data for 32 (63% yield) are as follows. 1H NMR (400 MHz, CDCl3):
δ 2.78 (d, J = 12.1 Hz, 1H, allyl), 3.02 (s, 3H, OMe), 3.05 (m, 1H), 3.07
(s, 3H, OMe), 3.16 (m, 1H), 3.35 (m, 1H), 3.47 (m, 2H), 3.56ꢀ3.76 (m,
4H), 4.01 (m, 2H), 4.72 (m, 2H), 5.56 (m, 2H), 6.06 (m, 1H), 6.24 (m,
1H), 7.00ꢀ7.06 (m, 4H, HAr), 7.20ꢀ7.43 (m, 18H, HAr), 7.65ꢀ7.77
(m, 8H, HAr) ppm. 31P NMR (161 MHz, CDCl3): δ 24.6, 25.4 ppm. IR
(neat): 1926 (Mn(CO)3), 2015 (Mn(CO)3). HRMS (MALDI TOF,
positive mode): m/z 655.0125 (M ꢀ Clꢀ), calcd for C31H27MnO4PPd
655.0062.
4.7. Synthesis of 33 and 34. The dimeric complex [(allyl)PdCl]2
(0.018 g, 0.05 mmol, 0.5 equiv) was introduced in a Schlenk tube. Then,
under N2, complex 15 (0.055 g, 0.09 mmol, 1 equiv) was added. After
addition of THF, the solution was stirred for 3 h at 40 °C and then
cooled to room temperature. AgPF6 (0.023 g, 0.09 mmol, 1 equiv) was
added. The mixture was stirred for 15 min and filtered. After concentra-
tion in vacuo, the yellow solid was isolated in 77% yield (0.029 g, 0.038
mmol).
C19H20O4ClNMn 416.0461.
Data for 27 (85% yield; method C) are as follows. H NMR (200
1
MHz, CDCl3): δ 3.58 (s, 3H, OMe), 3.64 (dd, 3J = 6.3 Hz, 4J = 2.6 Hz,
1H, H5), 4.38 (d, 3J = 6.3 Hz, 1H, H6), 6.16 (d, 4J = 2.6 Hz, 1H, H3), 6.71
(d, 3J = 3.6 Hz, 1H, HAr), 6.80ꢀ6.87 (m, 3H, HAr), 7.20ꢀ7.26 (m, 4H,
HAr), 9.84 (s, 1H, CHO) ppm. 13C NMR (100 MHz, CDCl3): δ 44.8
(C5), 50.7 (C6), 55.2 (OMe), 62.4 (C3), 72.2 (C1), 97.6 (C2), 126.5
(CHAr), 127.3 (CHAr), 127.4 (CHAr), 128.0 (CHAr), 129.0 (CHAr), 129.9
(CHAr), 140.4, 141.2, 145.5 (Cquat), 194.1 (CHO), 221.3 (Mn(CO)3)
ppm. IR (ATR Diamant): ν 1724 (CHO), 1906 (Mn(CO)3), 2008
(Mn(CO)3) cmꢀ1. HRMS (ESI, positive mode): m/z 456.9916 (M þ
Hþ), calcd for C21H15MnNaO5S 456.9918.
1
Data for 28 (50% yield; method C) are as follows. H NMR (400
MHz, CDCl3): δ 2.65 (s, 1H, OH), 3.48 (s, 4H, OMe and H5), 4.03 (d,
3J = 6.1 Hz, 1H, H6), 5.32 (m, 2H, H3 and HAr), 6.62 (t, 3J = 4.2 Hz, 1H,
HAr), 6.83 (d, 3J = 3.1 Hz, 4H, HAr), 7.03 (d, 3J = 7.4 Hz, 4H, HAr), 7.31
(m, 2H, HAr), 7.78 (m, 2H HAr), 7.59 (t, 3J = 7.4 Hz, 4H, HAr) ppm. 13
C
NMR (100 MHz, CDCl3): δ 43.3 (C5), 53.5 (C6), 54.7 (OMe), 61.5
(CAr), 73.4 (C3), 77.0 (CAr), 81.1 (CAr), 127.3 (CHAr), 127.4 (CHAr),
127.4 (CHAr), 127.7 (CHAr), 127.8 (CHAr), 127.9 (CHAr), 128.3
(CHAr), 128.6 (CHAr), 128.9 (CHAr), 130.3 (CHAr), 130.4 (CHAr),
131.1 (CHAr), 132.7 (CHAr), 137.9 (CAr), 139.8 (CAr), 142.4 (CAr),
142.5 (CAr), 143.4 (CAr), 148.3 (CAr) ppm. IR (ATR Diamant): ν 1926
(Mn(CO)3), 2013 (Mn(CO)3) cmꢀ1. HRMS (ESI, positive mode):
m/z 611.0750 (M þ Hþ), calcd for C33H25MnNaO5S 611.0701.
Data for 33 (77% yield) are as follows. 1H NMR (400 MHz, THF-d8;
tentative assignments due to low resolution): δ 3.15 (m, 6H, H1 þ H5 þ
2H8 þ 2Hallyl), 3.53 (m, 5H, OMe þ 2Hallyl), 3.95 (m, 1H, H6), 6.06 (m,
1H, allyl), 7.00ꢀ7.5 (m, 15H, PPh2 þ Ph) ppm. 31P NMR (161 MHz,
CDCl3): δ 32.0 (PPh2) ppm. IR (neat): 1934 (Mn(CO)3), 2016
(Mn(CO)3) cmꢀ1. Anal. Calcd: C, 54.56; H, 4.58. Found: C, 54.71;
H, 4.73.
1
Data for 29 (89% yield; method C) are as follows. H NMR (400
MHz, CDCl3): δ 3.33 (s, 3H, OMe), 5.54 (dd, 3J = 6.3 Hz, 4J = 2.3 Hz,
1H, H5), 4.34 (d, 3J = 6.3 Hz, 1H, H6),5.41 (d, 4J = 2.3 Hz, 1H, H3), 6.77
(d, 3J = 2.4 Hz, 1H, HAr), 6.84 (t, 3J = 5.1 Hz, 2H, HAr), 6.96 (dd, 3J = 7.6
Hz, 4J = 2.4 Hz, 2H, HAr),7.20 (m, 3H, HAr), 7.44 (m, 3H, HAr), 7.64
(dd, 3J = 5.4 Hz, 4J = 2.0 Hz, 2H, HAr). 13C NMR (100 MHz, CDCl3):
δ 44.7 (C5), 51.4 (C6), 54.7 (OMe), 64.9 (C1), 67.6 (C3), 103.6 (C2
or C17), 104.8 (C2 or C17), 125.9 (CHAr), 126.7 (CHAr), 127.5 (CHAr),
128.5 (CHAr), 128.8 (CHAr), 130.0 (CHAr), 135.9 (CHAr), 140.1 142.8,
146.0 (CAr). IR (ATR Diamant): ν 1919 (Mn(CO)3), 2016 (Mn-
(CO)3) cmꢀ1. Anal. Calcd: C, 60.71; H, 3.72. Found: C, 60.84; H, 3.89.
34 was prepared using the same experimental conditions as for 33, but
THF was replaced by CH2Cl2.
Data for 34 (64% yield) are as follows. 1H NMR (400 MHz, CD2Cl2;
tentative assignments due to low resolution): δ 3.25 (m, 6H, H1 þ H5 þ
2H8 þ 2Hallyl), 3.64 (s, 3H, OMe), 3.85 (m, 2H, Hallyl), 4.04 (m, 1H,
H6), 6.00 (m, 1H, Hallyl), 7.00ꢀ7.5 (m, 15H, HPPh2 þ HPh) ppm. 31
P
1
Data for 30 (83% yield; method C) are as follows. H NMR (200
MHz, CDCl3): δ 2.31 (s, 6H, NMe2), 3.02 (d, 2J = 13.1 Hz, 1H, H13a),
3.27 (d, 2J = 13.1 Hz, 1H, H13b), 3.54 (s, 3H, OMe), 3.61 (dd, 3J = 6.2
Hz, 4J = 2.3 Hz, 1H, H5), 4.27 (d, 3J = 6.2 Hz, 1H, H6), 5.90 (d, 4J = 2.3
Hz, 1H, H3), 6.74 (d, 3J = 3.5 Hz, 1H, HAr), 6.84ꢀ6.87 (m, 1H, HAr),
7.11ꢀ7.30 (m, 6H, HAr) ppm. 13C NMR (100 MHz, CDCl3): δ 44.7
(C5), 46.3 (NMe2), 51.2 (C6), 54.8 (OMe), 62.5 (C13), 69.2 (C1), 69.6
(C3), 108.3 (C2), 125.3 (CHAr), 126.7 (CHAr), 126.9 (CHAr), 127.5-
(CHAr), 128.4 (CHAr), 128.7 (CHAr), 141.3, 143.9 (CAr) ppm. IR (ATR
Diamant): ν 1918 (Mn(CO)3), 2002 (Mn(CO)3) cmꢀ1. HRMS (ESI,
positive mode): m/z 464.0722 (M þ Hþ), calcd for C23H23O4NMnS
464.0722.
NMR (161 MHz, CDCl3): δ 31.1 (PPh2), ꢀ142.9 (PF6) ppm. Anal.
Calcd: C, 47.60; H, 3.99. Found: C, 47.81; H, 4.14.
4.8. Resolution Procedure for Racemic Complexes (()-6,
(()-7, and (()-8: Synthesis and Separation of Diastereoiso-
meric Complexes 36,23 37, and 38. A mixture of the racemic
complex (0.4 mmol) and (S)-(þ)-bis(μ-chloro)bis[2-[(dimethyl-
amino)ethyl]phenyl-C2,N]dipalladium(II) (0.2 mmol, 0.5 equiv) in
toluene (3 mL) was stirred at room temperature for 1 h. After concentra-
tion in vacuo, the crude mixture was purified by flash chromatography on
silica gel to separate the diastereoisomeric mixture. In the case of 37,
attempts to separate the two diastereoisomers were unsuccessful.
Data for (S,3pR)-36 (34% yield) are as follows. de: 90%. Rf = 0.66
(Et2O). [R]D20 = þ45 cm3 gꢀ1 dmꢀ1 (c 0.23 g/100 mL, CHCl3). 1H
NMR (CDCl3): δ 1.84 (d, 3J = 6.6 Hz, 3H, H26), 2.69 (s, 3H, NMe),
2.76 (s, 3H, NMe), 2.89 (s, 3H, OMe), 3.36 (d, 3J = 6.4 Hz, 1H, H1), 3.47
1
Data for 31 (89% yield; method C) are as follows. H NMR (200
MHz, CDCl3): δ 3.43 (s, 3H, OMe), 3.50 (dd, 3J = 6.1 Hz, 4J = 2.5 Hz,
1H, H5), 4.17 (d, 3J = 5.1 Hz, H6), 5.15 (d, 4J = 2.5 Hz, 1H, H3), 5.85
(d, 3J = 3.5 Hz, 1H, HAr), 6.60 (dd, 3J = 5.1 Hz, 4J = 3.5 Hz, 1H, HAr),
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(t, 3J = 7.1 Hz, 1H, H5), 3.75 (t, 3J = 5.7 Hz, 1H, H25), 3.95 (t, 3J = 5.9 Hz,
1H, H6), 6.39ꢀ6.46 (m, 2H, HAr), 6.52 (t, 3J = 7.8 Hz, 1H, H4), 6.84 (t,
3J = 7.6 Hz, 1H, HAr), 6.93 (d, 3J = 7.0 Hz, 1H, HAr), 7.15ꢀ7.43 (m, 11H,
HAr), 7.65 (dd, 3J = 7.4 Hz, 3J = 12.0, 2H, HAr), 7.80 (dd, 3J = 7.3 Hz, 3
J = 11.9 Hz, 2H, HAr) ppm. 13C NMR (100 MHz, CDCl3): δ 21.7 (C26),
41.5 (C6), 43.1 (C1), 46.9 (NMe), 50.6 (NMe), 54.0 (OMe), 57.9 (d,
(C4 or CAr), 146.6 (C4 or CAr), 151.9 (CAr), 154.8 (CAr) ppm. 31P NMR
(162 MHz, CDCl3): δ 45.0 (PPh2) ppm. IR (ATR Diamant): ν 1909
(Mn(CO)3), 2013 (Mn(CO)3) cmꢀ1. HRMS (ESI, positive mode):
m/z 624.1642 ([M ꢀ Mn(CO)3 ꢀ Cl þ Hþ], calcd for C35H37NOPPd
624.1648.
Data for (S,1pS)-38 (32% yield) are as follows. Yellow crystals. de:
3JCP = 10 Hz, C5), 76.0 (C25), 80.1 (d, 1JCP = 47 Hz, C3), 105.3 (d, 2JCP
=
88%. [R]D = ꢀ140 cm3 gꢀ1 dmꢀ1 (c 0.6 g/100 mL, CHCl3). H
NMR (400 MHz, CDCl3): δ 1.63 (d, 3J = 6.7 Hz, 3H, Me), 2.62 (s, 3H,
NMe), 2.69 (s, 3H, NMe), 3.23 (m, 1H, H5), 3.34 (s, 3H, OMe), 5.79
(m, 2H, H6 and H25), 6.08 (t, 3J = 7.0 Hz, 1H, H3), 6.60 (d, 3J = 5.8 Hz,
1H, H2), 6.75 (m, 1H, HAr), 7.15 (m, 9H, HAr), 7.25 (m, 2H, HAr),
7.55 (m, 5H, HAr), 8.39 (m, 2H, HAr) ppm. 31P NMR (162 MHz,
CDCl3): δ 43.9 (PPh2). IR (ATR Diamant): ν 1914 (Mn(CO)3),
2020 (Mn(CO)3). HRMS (ESI, positive mode): m/z 624.1642 [M ꢀ
Mn(CO)3 ꢀ Cl þ Hþ], calcd for C35H37NOPPd 624.1648.
4.9. Decomplexation of (S,3pS)-36 and (S,3pR)-36. To one
of the diastereoisomers (S,3pS)-36 and (S,3pR)-36 (0.1 mmol) was
added a 0.1 M solution of ethylenediamine in chloroform (2 mL, 0.2
mmol) at room temperature, and the mixture was stirred for 10 min.
After concentration in vacuo, the crude mixture was purified by flash
chromatography on silica gel to afford (3pS)-6 and (3pR)-6 in 77 and
84% yields, respectively, with 90% ee. Under the same experimental
conditions, the enantioenriched (1pS)-8 and (1pR)-8 were isolated in
88% yield and with 88 and 86% ee starting from (S,1pS)-38 and (S,1pR)-
38.
20
1
22 Hz, C4), 122.4 (CHAr), 124.2 (CHAr), 125.4 (d, 3JCP = 5 Hz, CHAr),
126.4 (CHAr), 126.9 (d, 2JCP = 12 Hz, CHAr), 127.2 (CHAr), 128.3 (d,
2JCP = 11 Hz, CHAr), 128.9 (CHAr), 130.3 (d, 3JCP = 8 Hz, CHAr), 133.4
(d, 2JCP = 11 Hz, CHAr), 134.0 (CAr), 134.5 (CAr), 136.2 (d, 2JCP = 11
Hz, CHAr), 137.6 (d, 3JCP = 8 Hz, CHAr), 144.9 (C2), 147.1 (CAr), 152.9
(CAr), 154.6 (CAr) ppm. 31P NMR (161 MHz, CDCl3): δ 39.0 (PPh2)
ppm. IR (neat): 1925 (Mn(CO)3), 2014 (Mn(CO)3) cmꢀ1. HRMS
(ESI, positive mode): m/z 798.0568 (M þ Hþ), calcd for C38H37-
O4ClMnNPPd 798.0564.
Data for (S,3pS)-36 (40% yield) are as follows. de: 90%. Rf = 0.50
(Et2O). [R]D20 = ꢀ50 cm3 gꢀ1dmꢀ1 (c 0.21 g/100 mLꢀ1, CHCl3). 1H
NMR (400 MHz, CDCl3): δ 1.79 (d, 3J = 6.4 Hz, 3H, H26), 2.72 (s, 6H,
NMe2), 2.99 (s, 3H, OMe), 3.29 (tapp, 3J = 6.5 Hz, H5), 3.37 (d, 3J = 5.9
Hz, 1H, H1), 3.79 (t, 3J = 5.8 Hz, 1H, H25), 3.93 (t, 3J = 6.0 Hz, 1H, H6),
5.91 (t, 3J = 7.8 Hz, 1H, H4), 6.46 (t, 3J = 7.2 Hz, 1H, HAr), 6.59 (t, 3
J = 6.8 Hz, 1H, HAr), 6.84 (t, 3J = 7.2 Hz, 1H, HAr), 6.93 (d, 3J = 6.8 Hz,
3
1H, HAr), 7.08 (d, J = 7.2 Hz, 2H, HAr), 7.22ꢀ7.27 (m, 4H, HAr),
7.32ꢀ7.37 (m, 4H, HAr), 7.44 (d, 3J = 6.8 Hz, 1H, HAr), 7.72 (dd, 3J = 7.0
Hz, 3J = 11.9 Hz, 2H, HAr), 7.95 (dd, 3J = 7.4 Hz, 3J = 11.5 Hz, 2H, HAr)
ppm. 13C NMR (100 MHz, CDCl3): δ 21.1 (C26), 40.9 (C6), 41.9 (C1),
46.6 (NMe), 50.4 (NMe), 54.0 (OMe), 58.0 (d, 3JCP = 10.3 Hz, C5),
75.7 (C25), 78.6 (d, 1JCP = 46 Hz, C3), 103.6 (d, 2JCP = 10.3 Hz, C4),
(3pS)-6 (77% yield): [R]D20 = þ57 cm3 gꢀ1 dmꢀ1 (c 0.21 g/100 mL,
CHCl3).
(3pR)-6 (84% yield): [R]D20 = ꢀ58 cm3 gꢀ1 dmꢀ1 (c 0.21 g/100 mL,
CHCl3).
(1pS)-8 (88% yield): [R]D20 = ꢀ5.9 cm3 gꢀ1 dmꢀ1 (c 0.44 g/100 mL,
CHCl3).
3
122.6 (CHAr), 124.3 (CHAr), 125.7 (d, JCP = 5.1 Hz, CHAr), 125.9
(CHAr), 126.8 (d, 2JCP = 12 Hz, CHAr), 127.2 (CHAr), 128.4 (d, 2JCP
=
(1pR)-8 (88% yield): [R]D20 = þ7.2 cm3 gꢀ1 dmꢀ1 (c 0.4 g/100 mL,
CHCl3).
10.3 Hz, CHAr), 128.7 (CHAr), 128.9 (d, 3JCP = 5.1 Hz, CHAr), 129.9 (d,
3JCP = 2.6 Hz, CHAr), 130.4 (d, 3JCP = 2.6 Hz, CHAr), 134.2 (d, 2JCP = 12
Hz, CHAr), 135.8 (d, 2JCP = 12 Hz, CHAr), 137.0 (d, 2JCP = 10.3, CHAr),
145.5 (C2), 147.2 (CAr), 151.7 (CAr), 154.4 (CAr) ppm. 31P NMR (161
MHz, CDCl3): δ 39.0 (PPh2) ppm. IR (neat): 1920 (Mn(CO)3), 2011
(Mn(CO)3) cmꢀ1. HRMS (ESI, positive mode): m/z 798.0596 (M þ
Hþ), calcd for C38H37O4ClMnNPPd 798.0564.
(2pS)-3 (77% yield): [R]D20 = ꢀ1.5 cm3 gꢀ1 dmꢀ1 (c 0.20 g/100 mL,
CHCl3).
(3pR)-3 (65% yield): [R]D20 = þ1.5 cm3 gꢀ1 dmꢀ1 (c 0.17 g/100 mL,
CHCl3).
(2pS)-2 (96% yield): [R]D20 = ꢀ8.8 cm3 gꢀ1 dmꢀ1 (c 0.84 g/100 mL,
CHCl3).
Data for 37 (95% yield) are as follows. Mixture of diastereoisomers.
(2pR)-2(96% yield): [R]D20 = þ10.2 cm3 gꢀ1 dmꢀ1 (c 1.14 g/100 mL,
CHCl3).
3
3
1H NMR (400 MHz, CDCl3): δ (d, J = 7.3 Hz, 6H, Me), 1.78 (d,
J = 6.5 Hz, 3H, NMe), 2.34 (m, 2H, H1 or H5), 2.57 (m, 2H, H1 or H5),
2.61 (d, 3J = 6.5 Hz, 3H, NMe), 2.76 (s, 6H, OMe), 3.77 (m, 2H, H25),
6.45 (m, 4H, H3 and HAr), 6.82 (m, 2H, HAr), 6.92 (m, 2H, HAr), 7.35
(m, 24H, HAr), 7.72 (m, 4H, HAr), 7.87 (m, 4H, HAr) ppm. IR (ATR
Diamant): ν 1941 (Mn(CO)3), 2017 (Mn(CO)3) cmꢀ1. HRMS (ESI,
positive mode): m/z 762.0812 (M ꢀ Clþ), calcd for C38H36MnNO4PPd
762.0797.
(1pS)-10 (73%yield):[R]D20 =þ74.9 cm3 gꢀ1 dmꢀ1 (c0.94g/100 mL,
CHCl3).
(2pR)-10(73%yield): [R]D20 = ꢀ59 cm3 gꢀ1 dmꢀ1 (c 0.88 g/100 mL,
CHCl3).
(2pS)-15 (84%yield):[R]D20 =þ271 cm3 gꢀ1 dmꢀ1 (c 0.80 g/100 mL,
CHCl3).
(2pR)-15 (84%yield):[R]D20 =ꢀ259 cm3 gꢀ1 dmꢀ1 (c 1.16 g/100 mL,
CHCl3).
Data for (S,1pR)-38 (34% yield) are as follows. Orange crystals. de:
20
1
86%. [R]D = ꢀ103 cm3 gꢀ1 dmꢀ1 (c 0.8 g/100 mL, CHCl3). H
NMR (400 MHz, CDCl3): δ 1.47 (d, 3J = 6.6 Hz, 3H, Me), 2.42 (d, J =
2.4 Hz, 3H, NMe), 2.83 (d, J = 2.4 Hz, 3H, NMe), 3.29 (m, 1H, H5),
3.41 (s, 3H, OMe), 4.07 (m, 1H, H31), 3.79 (t, 3J = 5.8 Hz, 1H, H25),
5.83 (m, 3H, H6 and HAr), 6.13 (t, 3J = 7.2 Hz, 1H, H3), 6.67 (m, 2H,
H2 and HAr), 7.01 (d, 3J = 5.5 Hz, 2H, HAr), 7.08 (m, 5H, HAr), 7.27 (m
’ ASSOCIATED CONTENT
S
Supporting Information. CIF files giving crystallo-
b
1H, HAr), 7.34 (t, J = 13.7 Hz, 2H, HAr), 7.42 (d, J = 5.9 Hz, 1H,
HAr), 7.50 (dd, 3J = 7.6 Hz, 3J = 11.3 Hz, 2H, HAr), 8.13 (dd, 3J = 7.6
Hz, 3J = 11.3 Hz, 2H, HAr) ppm. 13C NMR (100 MHz, CDCl3): δ 13.8
(C32), 42.8 (NMe), 45.2 (d, 3JCP = 10 Hz, C5), 45.2 (d, 2JCP = 7.3 Hz,
C6), 48.8 (NMe), 54.8 (OMe), 67.3 (d, 3JCP = 10.0 Hz, C3), 71.4 (d,
graphic data for complexes 15, 33, 34, and 38 and a table
giving crystal data and refinement details for 15. This mate-
rial is available free of charge via the Internet at http://pubs.acs.
org.
3
3
1JCP = 31.5 Hz, C1), 73.7 (C31), 101.8 (d, JCP = 9.2 Hz, C2), 122.5
2
’ AUTHOR INFORMATION
(CHAr), 123.4 (CHAr), 125.2 (d, 3JCP = 5.5 Hz, CHAr), 126.9 (CAr), 127.3
(CHAr), 127.6 (CHAr), 127.7 (d, 2JCP = 10.5 Hz, CHAr), 128.3 (CHAr),
128.4 (CHAr), 128.5 (CHAr), 129.0 (CAr), 130.6 (CHAr), 131.6 (CHAr),
135.5 (d, 2JCP = 11.7 Hz, CHAr), 137.7 (d, 2JCP = 13.9 Hz, CHAr), 142.6
Corresponding Author
*E-mail: francoise.rose@upmc.fr (F.R.-M.); eric.rose@upmc.fr
(E.R.).
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Organometallics
ARTICLE
’ ACKNOWLEDGMENT
Rose, E.; Gꢀerard, H.; Herson, P. Organometallics 2008, 27, 2505.
(d) Eloi, A.; Rose-Munch, F.; Rose, E.; Chavarot-Kerlidou, M.;
Gꢀerard, H. Organometallics 2009, 28, 925.
(23) Cetiner, D.; Jacques, B.; Payet, E.; Chavarot-Kerlidou, M.;
Rose-Munch, F.; Rose, E.; Tranchier, J.-P.; Herson, P. Dalton Trans.
2009, 27.
(24) For the ortho-directing character of the Ph2P(O) group, see for
instance: Ariffin, A.; Blake, A. J.; Ewin, R. A.; Li, W. S.; Simpkins, N. S.
J. Chem. Soc., Perkin Trans. 1 1999, 3177.
(25) For the ortho-directing character of the Me2NCH2 group, see
for instance: Dickens, P. J.; Gilday, J. P.; Negri, J. T.; Widdowson, D. A.
Pure Appl. Chem. 1990, 62, 575.
We thank Dr. J.-P. Tranchier (IPCM, UMR 7201, Universitꢀe
P. and M. Curie, Paris) for helpful discussions, C. Mꢀeliet (USTL,
ENSCL, UMR 8181, Villeneuve d’Ascq) for NMR studies, and
the Ministꢁere de l’Education Nationale and de la Recherche for a
MENRT grant to D.C.
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