Phosphino-substituted (η5-cyclohexadienyl) tricarbonylmanganese complexes: Synthesis and structure

Article abstract of DOI:10.1039/c1nj20152b

The synthesis of phosphino derivatives built on a (η⁵- cyclohexadienyl)Mn(CO)₃ scaffold is efficiently performed using either a lithiation/electrophile quench sequence or a Pd-catalyzed coupling reaction. The structure of one of them

Full text of DOI:10.1039/c1nj20152b

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LETTER
Phosphino-substituted (g5-cyclohexadienyl)tricarbonylmanganese
complexes: synthesis and structurewz
Franc¸ oise Rose-Munch,* Derya Cetiner, Murielle Chavarot-Kerlidou and Eric Rose
Received (in Montpellier, France) 23rd February 2011, Accepted 25th March 2011
DOI: 10.1039/c1nj20152b
The synthesis of phosphino derivatives built on a (g5-cyclo-
hexadienyl)Mn(CO)3 scaffold is efficiently performed using
either a lithiation/electrophile quench sequence or a Pd-catalyzed
coupling reaction. The structure of one of them was established
by X-ray analysis.
For
(Z5-X-substituted-cyclohexadienyl)tricarbonylmanganese
complexes, X being a good leaving group such as Cl, OMe,
NR02, or SR00, treatment with a hydride and then an acid can
eliminate HX via cine and tele nucleophilic substitutions without
changing the hapticity of the complexes (Scheme 1b).3
More recently general functionalization methods of
(Z5-cyclohexadienyl)Mn(CO)3 derivatives allowed us to prepare
unprecedented Z5-Mn complexes. Indeed palladium-catalyzed
cross coupling reactions of (Z5-chlorocyclohexadienyl)Mn(CO)3
complexes (Scheme 2a),4 as well as lithiation/electrophilic quench
sequences of Z5-chloro- and (-bromocyclohexadienyl)Mn(CO)3
complexes (Schemes 2b and c),5 lead to efficient syntheses
of a large variety of diversely substituted Z5 complexes. These
different methodologies provide an easy synthesis of the corres-
ponding Z6 complexes after rearomatization by exo-hydride
abstraction at the sp3 carbon atom when R = H (Scheme 2d).
Finally, the first resolution of Z6-arene-Mn complexes was
reported very recently, and permits an access to enantiopure
cationic (Z6-arene)tricarbonylmanganese complexes via the
The electrophilicity of an arene is dramatically enhanced by
coordination to a tricarbonylmetal entity, M(CO)3 (M = Cr,
Mn+), allowing several transformations which cannot be carried
out on the metal-free arene ring. Thus there has been widespread
interest in the chemistry of arene-metal complexes and, among
them, Cr complexes have been extensively studied.1 More
recently, the isoelectronic cationic [(Z6-arene)Mn(CO)3]+
complexes have been taking a growing place in organo-
metallic chemistry as well as in organic synthesis.2 These
[(Z6-arene)Mn(CO)3]+ complexes easily add a nucleophile Rꢀ
to the arene ring and deliver (Z5-cyclohexadienyl)Mn(CO)3
derivatives which are neutral and very stable (Scheme 1a)
and whose properties have been extensively studied in our group.
Scheme 1 (a) Synthesis of Z5-Mn complexes and (b) one example of
cine nucleophilic substitution.
UPMC Univ Paris 06, IPCM, Institut Parisien de Chimie
´
Moleculaire, UMR CNRS 7201, Equipe de Chimie Organique et
Organometallique, 4, Place Jussieu, 75252 Paris Cedex 05, France.
´
E-mail: francoise.rose@upmc.fr; Fax: +33 (0)144275504;
Tel: +33 (0)144276235
w Dedicated to Professor Didier Astruc on the occasion of his
65th birthday and in token of a long faithful lasting friendship
(F. R.-M., E. R.).
z Electronic supplementary information (ESI) available: Detailed
crystallographic data for complex 6. CCDC reference number
813148. For ESI and crystallographic data in CIF or other electronic
format see DOI: 10.1039/c1nj20152b
Scheme 2 Reactivity of Z5-Mn complexes.
c
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coupling reaction4 which would use the chlorine atom at the
end of the Z5 system to substitute it by another coordinating
group such as a thienyl one.
Synthesis of complex 2 was easily achieved in 96% yield by
nucleophilic addition of PhMgCl to cationic (Z6-p-chloroanisole)-
Mn(CO)3 1,4a,11 regioselectively ortho to the chloride.12 The
best experimental conditions for the lithiation/electrophilic
quench sequence were determined in
a previous study
which revealed that the lithiation step was highly substrate
dependent.5a,b In the present case, complete conversion was
achieved by reaction with 1.6 equivalents of BuLi for 15 min at
ꢀ78 1C. After addition of 2 equivalents of PPh2Cl and usual
work up, two Z5 regioisomer complexes 3 and 4 were isolated
in an 85% overall yield, the major one, 3, recovered in 60%
yield corresponding to the substitution of the C2 carbon,
ortho to the chlorine atom (Scheme 5).
Scheme 3 Resolution of cationic (Z6-arene)tricarbonylmanganese
complexes.
round trip of a chiral auxiliary Nuꢀ* (Scheme 3).6 Indeed,
addition of Nuꢀ* (the camphor enolate) affords two diastereo-
isomers which can be separated by column chromatography.
Treatment of these diastereoisomers with AgBF4 and
CF3CO2H yields the enantiopure Z6 complexes with elimination
of the chiral auxiliary (Scheme 3).
Before attempting the palladium-catalyzed coupling reaction
with complex 3 that we considered as the best candidate to
form potential bidentate ligand, we tested the reaction on the
simple model complex 2 with no substituent on the Z5
cyclohexadienyl ring ortho or meta to the chlorine atom. Using
Pd2dba3, AsPh3 as the catalytic system,4a the thienyl derivative
ThSnBu3 readily reacted with complex 2 to deliver the
expected Z5 complex, whose chlorine atom was substituted
by the thienyl group, in a satisfying 89% yield (Scheme 6).
Under the same experimental conditions, complex 3 delivered
complex 6 bearing three substituents on the p system with two
adjacent potential ligands. The presence of the sterically
demanding PPh2 group does not decrease the yield which
maintains an 89% value (Scheme 6).
1H NMR spectra are in good agreement with the proposed
structures and the main chemical shifts of phosphino-
substituted complexes 3, 4, 6 as well as those of the starting
product 2 are compiled in Table 1. The H5 and H6endo protons
resonate at about the same frequencies for complexes 2, 3, 4
and 6 because the chemical environment is quite similar.
However, for the H2 protons of complexes 2 and 4, they
resonate at different frequencies. Indeed, the H2 proton of
complex 4 is shielded by the presence of the PPh2 group at the
C3 carbon, for the same reason the H3 proton of complex 3
resonates at a lower frequency. It is worthy to note that the
This discovery is greatly expanding the area of applications
of such complexes in the field of enantioselective syntheses of
organic compounds like, for example, enantiopure cyclo-
hexenones (Scheme 4, X = Br, Cl, H) as well as organometallic
complexes like enantiopure phosphino-substituted Z5 or Z6
tricarbonylmanganese complexes.
The phosphino-substituted complexes are noteworthy
because tricarbonylmetal containing planar chiral complexes
represent an original family of ligands for enantioselective
catalysis7 where the metal tripod not only creates the planar
chirality but plays also the role of a steric and electronic
modulator. Most of the examples of such non-metallocenic
structures reported to date rely on tricarbonylchromium
complexes1c,8 and more scarcely on cymantrene9 or cyrhetrene10
derivatives. In this article we wish to report the synthesis
of mono and bidentate phosphino derivatives, based on the
(Z5-cyclohexadienyl)Mn(CO)3 scaffold and the X-ray structure
of one of them.
The strategic approach was based on the use of Z5 complex
2 as the starting material. Its functionalization by coordinating
groups was possible by using two strategies. The first one was
related to the lithiation–electrophilic quench sequence5 using
PPh2Cl as the electrophile which would allow the introduction
of the phosphino group ortho to the chloride or to the methoxy
group. The second one involved
a palladium-catalyzed
Scheme 4 Enantioselective synthesis of cyclohexenones.
Scheme 5 Lithiation/electrophilic quench sequence.
c
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identification of the regioisomer with the phosphino group
located adjacent to the thienyl group. The presence of three
substituents on the ring does not modify the Z5 structure, with
five coplanar sp2 carbons, while the remaining sp3 carbon is
located 41.61 above this plane. The conformation of the
Mn(CO)3 tripod is in agreement with what is usually observed,
the sp3 carbon being eclipsed by one Mn–CO bond.13 The
sulfur atom is pointing in the direction of the Mn(CO)3 entity
whereas one of the phenyl groups of the phosphino substituent
is oriented in the direction opposite the Mn(CO)3 tripod.
In summary, the syntheses of phosphino-substituted
derivatives based on the (Z5-cyclohexadienyl)Mn(CO)3
skeleton have been achieved in good yields using either
lithiation/electrophilic quench sequences or Pd-catalyzed
reactions. The X-ray structure of one of them has been
described. Work is in progress to explore the coordination
properties of complexes 3, 4 and 6 toward a transition metal to
test them as ligands for homogeneous catalysis.
Scheme 6 Pd-catalyzed coupling reactions.
Table 1 H2,3,5,6 and P chemical shifts (in ppm) of complexes 2, 3, 4
and 6 in CDCl3
Complex
dH2
dH3
dH5
dH6
dP
Experimental section
2
3
4
6
5.23
—
4.64
—
5.57
4.88
—
3.58
3.54
3.70
3.50
4.32
4.45
4.43
4.17
—
General procedures
ꢀ4.4
ꢀ17.3
ꢀ6.5
All reactions were routinely performed under a dry nitrogen
atmosphere using standard Schlenk techniques. THF was
dried over sodium benzophenone ketyl and distilled. 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 ES-MS by the Groupe de Spectro-
5.15
P chemical shifts located at the C2 position of complexes 3 and
6 are very close, at ꢀ4.4 and ꢀ6.5 ppm, respectively, whereas a
strong difference is observed for the P chemical shift at the C3
position of complex 4 at ꢀ17.3 ppm. Besides the electronic
substituent effect, we suppose that the shift depends also on
the position of the P atom on the Z5 p system. Indeed we
already observed that the p system may have different electronic
effects on a substituent according to the position of this
substituent on the Z5-cyclohexadienyl ring.5c
metrie de Masse (IPCM, UMR 7201, UPMC).
´
(Z5-1-Chloro-2-diphenylphosphino-4-methoxy-6-phenylcyclo-
hexadienyl)tricarbonylmanganese 3. In a 50 mL two-neck
flask was introduced complex 2 (0.183 g, 0.51 mmol, 1 equiv.)
in THF (10 mL). The reaction mixture was cooled at ꢀ78 1C
and n-BuLi in hexane c = 1.6 mol Lꢀ1 (0.63 mL, 0.81 mmol,
1.6 equiv.) was added. After 15 min at ꢀ78 1C, ClPPh2
(0.182 mL, 1.02 mmol, 2 equiv.) was added and the reaction
mixture stirred at this temperature. Then, the reaction was
warmed at rt and water was added. The reaction mixture was
extracted with Et2O. The organic phase was washed with a
saturated solution of NaCl and dried by filtration on MgSO4.
Purification by column chromatography gave the two
regioisomers 3 (0.286 g, 0.66 mmol, 60%) and 4 (0.070 g,
0.13 mmol, 25%) as yellow powders.
Pleasingly, monocrystals of regioisomer 6 were readily
obtained for an X-ray diffraction study (X-ray data in
the ESIz). The ORTEP view shown in Fig. 1 confirms the
1
Complex 3 H NMR (400 MHz, CDCl3) d (ppm) 3.46 (s,
3H, OMe), 3.54 (dd, 3J = 6.3 Hz, 4J = 2.8 Hz, 1H, H5), 4.45
(d, 3J = 6.3 Hz, 1H, H6), 4.88 (d, 4J = 2.8 Hz, 1H, H3),
6.92–6.94 (m, 4H, HAr), 7.06 (m, 2H, HAr), 7.2 (m, 1H, HAr),
7.34–7.46 (m, 8H, HAr). 13C NMR (100 MHz, CDCl3) d (ppm)
43.2 (C5), 53.6 (C6), 55 (OMe), 68.6 (C3), 83.1 (d, JCP
=
2
25 Hz, C1), 106.7 (d, JCP = 20 Hz, C2), 126.9 (CHAr), 127.9
1
3
(CHAr), 128.6 (d, JCP = 8 Hz, CHAr), 128.8 (CHAr), 129.2
(CHAr), 129.3 (d, 3JCP = 7 Hz, CHAr), 130.3 (CHAr), 133.5 (d,
Fig. 1 Molecular structure of complex 6 with thermal ellipsoids at the
30% probability level. Selected bond lengths (A): Mn–C1: 2.211(2);
Mn–C2: 2.164(2); Mn–C3: 2.162(2); Mn–C4: 2.220(3); Mn–C5:
2.247(3); C2–P: 1.872(2). Selected bond angle (1): (C1C2C3C4C5)/
(C1C6C5): 41.6(2).
2JCP = 21 Hz, CHAr), 134 (d, JCP = 16 Hz, CHAr), 134.6
1
1
2
(d, JCP = 8 Hz, CAr), 135.7 (d, JCP = 21 Hz, CHAr), 141.7
(d, 3JCP = 2 Hz, C4), 142.3 (CAr), 221.5 (Mn(CO)3). 31P NMR
(162 MHz, CDCl3) d ꢀ4/4 ppm. IR (ATR Diamant) n 1926
c
2006 New J. Chem., 2011, 35, 2004–2008
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(Mn(CO)3), 2014 (Mn(CO)3) cmꢀ1. HRMS (MALDI TOF,
positive mode) m/z calc. for C28H22ClMnO4P 543.0325.
Found 543.0323 [M + H+]. Anal. Calc C: 61.95; H: 3.90%.
Found C: 61.87; H: 3.79%.
(Mn(CO)3) cmꢀ1. HRMS (ESI, positive mode) m/z calc. for
C32H25O4MnPS, 591.0585; found, 591.0586 [M + H+]. Anal.
Calc. C: 65.09; H: 4.10%. Found C: 64.97; H: 3.94%.
Complex 4 1H NMR (200 MHz, CDCl3) d (ppm) 3.41
3
3
(s, 3H, OMe), 3.7 (dd, J = 6.6 Hz, 1H, H5), 4.43 (d, J =
Acknowledgements
6.6 Hz, J = 1.6 Hz, 1H, H6), 4.64 (d, J = 1.6 Hz, 1H, H2),
7.06–7.13 (m, 2H, HAr), 7.29–7.60 (m, 8H, HAr). 13C NMR
(100 MHz, CDCl3) d (ppm) 43.9 (C5), 51.7 (C6), 55.6 (OMe),
4
4
We thank Dr J. P. Tranchier (UPMC Univ Paris 06, IPCM,
CNRS UMR 7201) for helpful discussions, L.-M. Chamoreau
(UPMC Univ Paris 06, IPCM, CNRS UMR 7201, Centre de
78.4 (d, 1JCP = 25 Hz, C3), 79.1 (C1), 95.2 (C2), 126.2 (CHAr),
Resolution des Structures) for the X-ray structure analysis,
´
127.9 (CHAr), 128.8 (d, JCP
= 7
Hz, CHAr), 128.9
3
CNRS for financial support and the Ministere de l’Education
Nationale et de la Recheche for a MENRT grant to DC.
(CHAr), 129.2 (d, JCP = 7 Hz, CHAr), 129.3 (CHAr), 130.2
3
(CHAr), 133.6 (d, JCP = 20 Hz, CHAr), 134.4 (d, JCP
=
2
1
12 Hz, CHAr), 135.4 (d, JCP = 21 Hz, CHAr), 136.9 (d,
2
1JCP = 13 Hz, CAr), 143.8 (CAr), 144.8 (d, 2JCP = 15 Hz, C4).
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3
CDCl3) d (ppm) 3.52 (s, 3H, OMe), 3.70 (dd, J = 6.1 Hz,
4J = 2.4 Hz, 1H, H5), 4.60 (d, 3J = 6.3 Hz, 1H, H6), 5.58 (dd,
4
3
3J = 5.8 Hz, J = 1.3 Hz, 1H, H2), 5.74 (dd, J = 6.1 Hz,
4J = 2.4 Hz, 1H, H3), 6.86 (d, 3J = 3.2 Hz, 2H, HAr),
7.10–7.25 (m, 6H, HAr). 13C NMR (100 MHz, CDCl3)
d (ppm) 42.4 (C5), 44.7 (C6), 54.7 (OMe), 65.6 (C3), 69.6
(C1), 90.4 (C2), 122.8 (CHAr), 124.7 (CHAr), 126.1 (CHAr),
126.9 (CHAr), 127.3 (CHAr), 128.8 (CHAr), 142.0 (CAr), 145.3
(CAr), 145.8 (CAr), 222.6 (Mn(CO)3). IR (ATR Diamant)
n 1923 (Mn(CO)3), 2005 (Mn(CO)3) cmꢀ1. Anal. Calc. for
C20H15MnO4S, C: 59.12; H: 3.72%. Found C: 59.54;
H: 3.81%.
(Z5-1-Thienyl-2-diphenylphosphino-4-methoxy-6-phenylcyclo
hexadienyl)tricarbonylmanganese 6. The same experimental
conditions as those for 5 were used. Yellow powder (0.137 g,
0.23 mmol, 86%). 1H (200 MHz, CDCl3) d (ppm) 3.43 (s, 3H,
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OMe), 3.50 (dd, J = 6.1Hz, J = 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, J = 5.1 Hz, J = 3.5 Hz, 1H,
HAr), 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). RMN 13C (100 MHz,
CDCl3) d (ppm) 43.4 (C5), 51.5 (C6), 54.7 (OMe), 70.3 (C3),
71.7 (d, 2JCP = 24 Hz, C1), 110.8 (d, 1JCP = 40 Hz, C2), 125.8
(CHAr), 126.7 (CHAr), 127.8 (CHAr), 127.9 (CHAr), 128.3 (d,
3
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2JCP = 8 Hz, CHAr), 128.4 (CHAr), 129.0 (d, JCP = 7 Hz,
2
CHAr), 129.2 (CHAr), 130.1 (d, 3JCP = 3 Hz, CHAr), 134.3 (d,
2JCP = 21 Hz, CHAr), 134.7 (CAr), 135.6 (d, JCP = 20 Hz,
2
CHAr), 136.5 (d, JCP = 8 Hz, CAr), 141.8 (CAr), 142.1 (d,
1
1JCP = 5 Hz, CAr), 144.8 (CAr). RMN 31P (162 MHz, CDCl3):
d ꢀ6.5 (PPh2). IR (ATR Diamant) n 1925 (Mn(CO)3), 2010
c
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New J. Chem., 2011, 35, 2004–2008 2007

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