Cyclopentadienyl-Ruthenium Catalysts
--- One Group of Ru(II) Complexes
Huijun ZHANG
2007-07-13
1
Content
Introduction
Cyclopentadienes
Cyclopentadienyl-Ruthenium
Their Applications
Outlook
2
Content
Introduction
Cyclopentadienes
Cyclopentadienyl-Ruthenium
Their Applications
Outlook
3
Ruthenium Complexes
Electron configuration: (Kr)4d75s1
Oxidation states: 2,3,4,6,8
“Ruthenium complexes have a variety of useful characteristics
including high electron transfer ability, high Lewis acidity, low
redox potentials, and stabilities of reactive metallic species such
as oxometals, metallacycles, and metal carbene complexes."
Naota, T.; Takaya, H.; Murahashi, S.-I. Chem. Rev. 1998, 98, 2599.
4
Ruthenium Complexes
Naota, T.; Takaya, H.; Murahashi, S.-I. Chem. Rev. 1998, 98, 2599.
5
Cyclopentadienyl-Ruthenium Complexes
Ruthenium-Catalyzed Reactions
—A Treasure Trove of Atom-Economic Transformations
Trost, B. M.; Frederiksen, M. U.; Rudd, M. T.
Angew. Chem., Int. Ed. Engl. 2005, 44, 6630
6
Cyclopentadienyl-Ruthenium Complexes
Cp- and Cp*-Ru(II) Complexes:
R
R
R
R
R
Ru
R
Cl
R
R
R
Ru
MeCN
MeCN
[PF6]
R
NCMe
Relationship between Structures and Reactivities:
Dérien, S.; Dixneuf, P. H. J. Organomet. Chem. 2004, 689, 1382
Bruneau, C.; Renaud, J-L.; Demerseman, B. Chem. Eur. J. 2006, 12, 5178
7
Content
Introduction
Cyclopentadienes
Cyclopentadienyl-Ruthenium
Their Applications
Outlook
8
Key Features of Cp Ligands
• The M-Cp bond dissociation is large (ferrocene is
stable to 400 oC).
• The ligand blocks several coordination sites.
• The ligand tends not to get involved chemically
(although it certainly can from time to time).
• It has excellent NMR properties.
9
C 5H 4R
Petroleum
Industry
+
rt.
~150oC
H
R
Unmethylated Cyclopentadienes
Okuda, J. Top. Curr. Chem. 1992, 160, 97.
Halterman, R. L. Chem. Rev. 1992, 92, 965.
10
C5HMe4R
H
2
R
OH
RCOOEt
Li
R=Me, Et, nPr, nBu and Ph
R=iPr
R=CF3
R: containing terminal functional groups
H+
R
-H2O
H
J. Organomet. Chem. 1977, 136, 1.
Org. Synth. 1987, 65, 42.
J. Organomet. Chem. 1998, 559, 181.
J. Am. Chem. Soc. 1992, 114, 6942.
Synthesis 1993, 684.
11
C5HMe4R
O
O
2 MeCHO
O
R=Me
R=CH2CH2CH=CH2
R=tBu
H+
-H2O
O
1) RLi
R
2) H+, -H2O
H
J. Organomet. Chem. 1983, 243, 119.
Organometallics 1988, 7, 1828.
Inorg. Synth. 1992, 29, 193. .
J. Organomet. Chem. 1988, 344, C1-C4.
J. Organomet. Chem. 1996, 520, 265.
12
C5H2R1R2R3CO2Et
O
CO2Et
CO2Et
NaHCO3
R1
PPh3Br
R1
PPh3
R
EtO2C
R1
X
PPh3
R3
R3
2
R2
EtO2C
R1
Hatanaka, M; Himeda, Y.; Ueda, I. J. Chem. Soc., Chem. Commun. 1990, 526.
13
C5HR4R’
Cp2ZrCl2
2 n-BuLi
Toluene
-78oC, 1h
R
Cp2ZrBu2 2
R
R
ZrCp2
R
R
R'CHO/AlCl3
[ClAlO]
R
R
R
rt, 1h
R
H
R'
R
regioisomers about
the double bonds
R: Me, Et, n-Pr, n-Bu, Ph···
R’CHO: aliphatic or aromatic aldehyde
Xi, Z.; Li, P. Angew. Chem., Int. Ed. Engl. 2000, 39, 2950.
14
Recent Two Examples
R2
1
R
4
R
PtCl2( 0.05 equiv)
4-A M.S., ClCH2CH2Cl, rt.
R1
R3 or Ph3PAuCl(2.0mol%), AgSbF6(2.0mol%) R4
CH2Cl2, 0oC
R2
R3
Funami, H.; Kusama, H.; Iwasawa, N. Angew. Chem. Int. Ed. 2007, 46, 909.
Lee, J. H.; Toste, F. D. Angew. Chem. Int. Ed. 2007, 46, 912.
15
Content
Introduction
Cyclopentadienes
Cyclopentadienyl-Ruthenium
Their Applications
Outlook
16
[Ru(η5-C5R5)(MeCN)3]+ Complexes
"RuCl3 3H2O"
+ C5HMe5
MeOH
reflux
[Ru(C5Me5)Cl2]2
III
[PF6]
Zn, KPF6
MeCN
Ru
LiBHEt3 THF
KPF6
MeCN
MeCN
MeCN
NCMe
[Ru(C5Me5)Cl]4
II
Fagan, P. J.; Ward, M. D.; Calabrese, J. C. J. Am. Chem. Soc. 1989, 111, 1698
Steinmetz, B.; Schenk, W. A. Organometallics 1999, 18, 943
17
Mbaye, M. D.; Demerseman, B.; Renaud, J.-L.; Toupet, L.; Bruneau, C.
Adv. Synth. Catal. 2004, 346 (7), 835
[Ru(η5-C5R5)(MeCN)3]+ Complexes
[(C6H6)RuCl2]2
[PF6]
[PF6]
1) TlCp, rt
MeCN
MeCN
hv.
Ru
2) NH4PF6
Ru
MeCN
MeCN
R
NCMe
COOEt [PF6]
Ru
MeCN
MeCN
Me
NCMe
R= Ph or Me
T. P. Gill, K. R. Mann, Organometallics 1982, 1, 485.
Komatsuzaki, N.; Uno, M.; Kikuchi, H.; Takahashi, S. Chem. Lett. 1996, 677.
18
Ru(η5-C5R5)(η4-diene)Cl complexes
"RuCl3 3H2O"
COD
[Ru(H2NNMe2)3(COD)(H)Cl]+
COD = 1,5-cyclooctadiene
1/x [Ru(COD)Cl2]x
KC9H7
CpTl
CCl4
Ru
H
Ru
Ru
Cl
Cl
Alvarez, P.; Gimeno, J.; Lastra, E.; Garcia-Granda, S.; Van der Maelen, J. F.;
Bassetti, M. Organometallics 2001, 20, 3762
19
Albers, M. O.; Robinson, D. J.; Shaver, A.; Singleton, E. Organometallics 1986, 5, 2199
Content
Introduction
Cyclopentadienes
Cyclopentadienyl-Ruthenium
Their Applications
Outlook
20
Cp-Ru Catalyzed C-C Bond
Formation Reactions
• Reactions Involving Ruthenacyclopentanes,
Ruthenacyclopentenes, Ruthenacyclopentadienes
• Heteroatom Additions to Alkynes
• Reactions Involving Additions of Diazo Compounds
• Reactions Initiated by Hydrometalations
• Regioselective Allylation of Nuclephiles
• Reactions Initiated by C-H Bond Activation
21
Reactions Involving Ruthenacyclopentanes
O
R
10% CpRuCl(cod)
+
R'
15% CeCl3 7H2O
DMF, 60oC
O
O
R
O
R
R'
R
R'
+
R'
Ru
+
+
Ru
R
H
O
O
R
Ru
R'
R'
+
H
R
H
Ru
O
R'
Trost, B. M.; Pinkerton, A. B. J. Am. Chem. Soc. 1999, 121, 4068.
22
Reactions Involving Ruthenacyclopentane
HO
+
10% CpRu(CH3CN)3PF6
O
15% CeCl3 7H2O
DMF, 60oC
O
O
[Ru+
HO
O
2
Trost, B. M.; Pinkerton, A. B. J. Am. Chem. Soc. 1999, 121, 10842.
Trost, B. M.; Pinkerton, A. B.; Kremzow, D. J. Am. Chem. Soc. 2000, 122, 12007.23
Reactions Involving Ruthenacyclopentane
OAc
96
+
OAc
MeOH, 100oC
[Ru+
:
0.7% Cp*RuCl(cod)
+
OAc
4
OAc
H
+
[Ru+
OAc
H
H
Fujiwhara, M.; Nishikawa, T.; Hori, Y. Org. Lett. 1999, 1, 1635.
24
Reactions Involving Ruthenacyclopentene
An Alder-Ene Type Reaction:
R
R'
+
[Ru
[Ru
[Ru+
R'
R
H
R
[Ru+
H
R'
R
R'
R'
R
Branched
Linear
n
Bu
n
H
n
n
Bu +
Bu
Bu
B
n
L
10% CpRu(COD)Cl
20% NH4PF6
MeOH, reflux
+
n
Bu
Bu
B/L= 5.2/1
Trost, B. M.; Indolese, A. J. Am. Chem. Soc. 1993, 115, 4361.
Trost, B. M.; Indolese, A. F.; Mu¨ ller, T. J. J.; Treptow, B. J. Am. Chem. Soc. 1995, 117,25615.
Reactions Involving Ruthenacyclopentene
O
5
O
10% CpRuCl(cod)
OH
MeO2C
MeOH, 60oC
5
O
HO
O
[Ru+
R'
MeO2C
HO
[Ru2+
R'
MeO2C
-
Trost, B. M.; Müller, T. J. J. J. Am. Chem. Soc. 1994, 116, 4985.
26
Reactions Involving Ruthenacyclopentene
O
OH
4
2.3
CO2Me
10% CpRu(CH3CN)3PF6
:
O
DMF, rt
4
4
MeO2C
1
CO2Me
H
[Ru+
4
HO
CO2Me
Trost, B. M.; Martinez, J. A.; Kulaweic, R. J.; Indolese, A. F. J. Am. Chem. Soc. 1993, 115,2710402.
Reactions Involving Ruthenacyclopentene
OH
+
R
5% Cp*RuCl(COD)
R
neat, r.t., 15min
R
CHO
major
+
CHO
Ph
85%(75/25)
CHO
But
CHO
60%(100/-)
MeOH2C
CHO
70%(76/24)
De´rien, S.; Dixneuf, P. H. J. Chem. Soc. Chem. Commun. 1994, 2551.
28
Reactions Involving Ruthenacyclopentene
1% Cp'Ru(CH3CN)3PF6
MeOH, rt
OH
O
CO2Et
Cp' =
HO
[Ru+
HO
[Ru+
29
Matsushima, Y.; Kikuchi, H.; Uno, M.; Takahashi, S. Bull. Chem. Soc. Jpn. 1999, 72, 2475.
Kikuchi, H.; Uno, M.; Takahashi, S. Chem. Lett. 1997, 1273.
Reactions Involving Ruthenacyclopentadiene
MeO2C
MeO2C
1% Cp*RuCl(cod)
O
MeO2C
O
MeO2C
, 40oC
R'
+
R'
Ru
+
+
Ru
Ru
R
+
R'
R
R'
Ru
R
R'
Yamamoto, Y.; Kitahara, H.; Ogawa, R.; Itoh, K J. Org. Chem. 1998, 63, 9610.
Yamamato, Y.; Kitahara, H.; Ogawa, R.; Kawaguchi, H.; Tatsumi, K.; Itoh, K. 30
J. Am. Chem. Soc. 2000, 122, 4310.
Heteroatom Additions to Alkynes
Additions of Water
O
NC(H2C)3
O
+
R'
R
5% CpRuCl(cod)
+
H+
Ru
NH4PF6, In(OTf)3
+
DMF/H2O 1/1, 100oC
Ru
RO
NC(H2C)3
O
R
R'
R
+
Ru
O
O
O
H 2O
H+
+
+
O
Ru
R'
Ru
R
R
OH
O
+
R'
O
O
Ru
R
Trost, B. M.; Krause, L.; Portnoy, M. J. Am. Chem. Soc. 1997, 119, 11319.
31
Heteroatom Additions to Alkynes
Intramollecular Version
O
10% CpRu(CH3CN)3OPF6
R
CSA, H2O
O
acetone, rt
H3CO2C
H3CO2C
H3CO2C
H3CO2C
O
Ph
R
R'
O
R'
Ph
O
+
H3CO2C
H3CO2C
5% CpRu(CH3CN)3PF6
acetone, rt
Ru
R
+
R
O
O
Ru Ph
H
O
R'
O
R'
+
R
R
Ru
O
R'
Ru
Ru
O
R'
+
HO R
+
H2O
O
R'
Trost, B. M.; Brown, R. E.; Toste, F. D. J. Am. Chem. Soc. 2000,122, 5877.
32
Heteroatom Additions to Alkynes
Additions of Halides
CN
O
10% CpRuCl(cod)
CN
+
SnCl4,5H2O, N(CH3)4Cl
DMF, 60oC
8.2:1, E:Z
O
Cl
O
O
Ru+ +
X
R
X- + R
R
Z
X
R
X
R
R
X
E
Ru
RuX
Ru+X-
R
Ru
O
O
Trost, B. M.; Pinkerton, A. B. J. Am. Chem. Soc. 1999, 121, 1988.
33
Heteroatom Additions to Alkynes
Additions of Carboxylic Acids
OCH3
H3CO
H3CO
Cp*RuCl(cod)
+
dioxane, rt
CH3COOH
O2CCH3
H3CCO2
+
R
R
R
Ru
+
+
H
R
Ru
O2CCH3
R
Ru
R
R
2+
CH3CO2H
H
R
Ru
R
-
O2CCH3
Le Paih, J.; Monnier, F.; Dérien, S. J. Am. Chem. Soc., 2003, 125, 11964.
34
Reactions Involving Additions of
Diazo Compounds
OH
SiMe3
2
+
N2
dioxane, 60oC
R'
SiMe3
R'
R
Me3Si
OH
Me3Si
5% Cp*RuCl(cod)
N2
SiMe3
SiMe3
R
Ru
Cl
Ru
SiMe3
Cl
R
R'
SiMe3
Cl
Ru
SiMe3
R
R
Ru
Cl
N2
SiMe3
Ru
Cl
R'
R
SiMe3
R'
SiMe3
R'
35
Le Paih, J.; Dérien, S.; Özdemir, I.; Dixneuf, P. H. J. Am. Chem.Soc. 2000, 122, 7400.
Reactions Initiated by Hydrometalations
Ph
Ph
D
5% Cp*RuCl(cod)
O
O
EtOD, rt
Ph
Ph
D
Ru D
D
O
O
Ru
Ru
H
Ph
Ru
O
D
Le Paih, J.; Rodrı´guez, D. C.; De´rien, S.; Dixneuf, P. H. Synlett 2000, 95.
36
Regioselective Allylation of Nuclephiles
Ph
OCO2Me + HN
Cp*RuCl(COD)
N
+ Ph
0oC, THF
N
L
B
:
16
84
(overall yield 99%)
Kondo, T.; Ono, H.; Satake, N.; Mitsudo, T.; Watanabe, Y. Organometallics 1995, 14, 1945.
OCO2tBu
Ph
+
1% catalyst
MeO2C
CO2Me
+
DMF, rt.
CO2Me
Ph
Ph
NaCH(CO2Me)2
CO2Me
B
L
[CpRu(NCCH3)3]PF6
1
2
[Cp*Ru(NCCH3)3]PF6
9
1
Trost, B. M.; Fraisse, P. L.; Ball, Z. T.; Angew. Chem. Int. Ed. 2002, 41, 1059. 37
Oxidative Addition of Allylic Substrate
Ru
X
Ph
Ph
X
Nu-
X
Ph
Nu
and
2L
2L
Ph
X-
Ru
X
L
Nu
L
Key Step in Ruthenium-Catalysed Allylic Substitution Reactions
Bruneau, C.; Renaud, J-L.; Demerseman, B. Chem. Eur. J. 2006, 12, 5178
38
Planar Chiral Ruthenium Catalysts
O
[PF6]
R
O
Ru
Ph
Ph
OCO2Et
+ NuNa
P
Ar Ar
(5 mol%)
THF, 20oC, 6h
Ph
Ph
Nu
>
MeCN
MeCN
>
63% ee 97%
NuNa= NaCH(CO2Me)2, NaCH(CO2Et)2, NaCMe(CO2Me)2
R= Me, Ph, tBu; Ar= Ph, o-MeC6H4, 3,5-Me2C6H3
Matsushima, Y.; Onitsuka, K.; Kondo, T.; Mitsudo, T.; Takahashi, S.
J. Am. Chem. Soc. 2001, 123, 10405.
39
Reactions Initiated by C-H Bond Activation
TBDMSO
COOEt
TBDMSO
COOEt
10% CpRu(CH3CN)3PF6
DMF, rt
EtOOC
TBDMSO
TBDMSO
+
COOEt
Ru
+
+
EtOOC
TBDMSO
Ru
H
TBDMSO
Ru
COOEt
+
+
TBDMSO
Ru H
COOEt
TBDMSO
COOEt
Ru
Trost, B. M.; Toste, F. D. J. Am. Chem. Soc. 1999, 121, 9728.
40
Content
Introduction
Cyclopentadienes
Cyclopentadienyl-Ruthenium
Their Applications
Outlook
41
Outlook
“Teaching An Old Dog New Tricks”
R
R
R
R1 2
* R
R
R3
R
R
[Ru
R
R
R
[Ru
R
R
R
[Ru R
etc.
n
[Ru: RuCl(COD), Ru(NCMe)3+, RuHL2
• New sterically demanding catalysts with bulky, electron
rich C5R5 ligands
• New optically active catalysts with chiral C5R4R* ligands
• Polymerizable catalysts for the recovery and recycling of
catalysts.
42
Acknowledgement
Prof. Zhenfeng Xi, Prof. Zhiping Li
Prof. Pierre Dixneuf, Dr. Christian Bruneau,
Dr. Bernard Demerseman
All Professors in the Institute of Organic Chemistry
All my lab mates
Peking U. Team:
Rennes U. Team:
Laboratoire de Catalyse
et Organométalliques
43
Thank you for your attention!
44
Proposed Mechanism
L.A.
O
R
H
[ClAl=O]n
R
H
O
path a
R
L.A.
O
ZrCp2
R
L.A.
Cp2ZrCl2
H
R
path b
O
ZrCp2
R
L.A.
R
H
Cp2Zr=O
O
ZrCp2
L.A.
45
Ruthenium Hydride
RuIIClLn
- Cl
RuIILn
CH3CH2OH
+
H3CHC OH
+
H RuIILn
H
¦Â-H elimination
II
Ru Ln
-CH3CHO
-H+
46