Post on 12-Jul-2022
Colloque Chimie durable
18 et 19 septembre 2012 - Ecole Normale Supérieure de Lyon
Environmentally friendly catalysis using polydentate ligands: low-loading palladium catalysts and copper-adducts
for (C−H, or N−H) and (C−Cl, or C−Br) functionalization
Jean-Cyrille Hierso
Dominique Lucas Henri Doucet
Institut de
Chimie Moléculaire
UMR 6302
Institut des
Sciences Chimiques
UMR 6226
2
Admitted “Green” chemistry principles
1. Prevention
2. Atom Economy Synthetic methods should be designed to maximize the incorporation of materials into the final product.
3. Less Hazardous Chemical Syntheses
4. Designing Safer Chemicals
5. Safer Solvents and Auxiliaries
6. Design for Energy Efficiency
7. Use of Renewable Feedstocks
8. Reduced Derivatization Unnecessary derivatization should be minimized or avoided.
9. Catalysis Catalytic reagents, as selective as possible, are preferred to stoichiometric reagents.
10. Design for Degradation
11. Real-time analysis for Pollution Prevention
12. Inherently Safer Chemistry for Accident Prevention
13. It is better to understand what you are doing than not...
Some issues addressed (or at least attempted !) in this ANR program…
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• R. B. Bedford et al. Chem. Commun. 1998, 2095.
• W. A. Herrmann et al. Angew. Chem. Int. Ed. EngI. 1995, 34, 1844.
• H. Doucet, M. Santelli et al. Chem. Commun. 2001, 325.
M. Beller et al. Angew. Chem. Int. Ed. EngI. 1995, 34, 1848.
Pd
P
oTol oTol
O
O
OPd
O P
oToloTol
PCy2 P(t-Bu)2
Ph2PPh2P
PPh2PPh2
Pd
Cl
PdCl P
O
OArArO
PO
ArO OAr
Ar = 2,4-(t-Bu)2C6H3
t-Bu
t-Bu
t-Bu
t-Bu
R. B. Bedford et al. Tetrahedron Lett. 1998, 39, 9793.
• S. L. Buchwald et al. Angew. Chem. Int. Ed. EngI. 1999, 38, 2413.
H. Doucet M. Santelli et al. J. Org. Chem. 2001, 66, 5923.
Milestones in low-loading catalysis
S. L. Buchwald et al. J. Am. Chem. Soc. 1999, 121, 9550.
Heck 100% (0.5x10-3%); Suzuki 74% (10-3%)
Heck 57% (10-5%); Suzuki 100% (10-4%)
Suzuki 91% (10-6%)
Heck 78% (10-6%); Suzuki 96% (10-6%)
J.-C. Hierso et al. Eur. J. Inorg. Chem. 2007, 3767: palladium cross-coupling, a review.
Ferrocene platform for implantation of phosphorus donors
Modular approach for library
building
4
“ Novel catalytic effects from cooperation of more than two donor atoms ? “
…what can be found beyond hemilability and chelating effects ?
5
PPh2
PPh2
Fet-Bu
Ph2P
PPh2
PPh2
Fe
t-Bu
P(i-Pr)2
PPh2
PPh2
Fet-Bu
PO
O
PPh2
PPh2
Fe
Me
Me
Me PPh2
Me
Me
Me
Me
PPh2
PPh2
Fet-BuPPh2
PPh2
Fe
Me
Me
Me
PPh2Fe
Ph2PPPh2
PPh2
Fet-Bu
CHO
PPh2
Me
Fe
Me
Me
Me PPh2
Me
Me
Me
Me
PO
O
Fe
PO
O
PO
O
Fe
PPh2
PR2
Fet-Bu
PR2
t-Bu
R = Ph, Me
Fu
PPh2
PPh2
Fe
Me
Me
Ph2P Me
Me
Ph2P
Me
Me PPh2
PPh2
Fe
t-Bu
PPh2
t-Bu PPh2
FePh2P
Ph2P PPh2
PPh2PPh2
PPh2
Fe
t-Bu
PPh2
PPh2
Polyphosphines built on ferrocene backbone
J.-C. Hierso et al. Chem. Soc . Rev. 2007, 36, 1754. A 1st generation library
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XR1
X = Br, Cl
R1R2
R2
H
R1 R2
R1R2
R2
H
(HO)2B R2
Pd/L2 Pd/L1
L2 = PPh2
PPh2
Fet-Bu
(i-Pr)2P
L1 = PPh2
PPh2
Fet-Bu
PPh2
t-Bu PPh2
TONs up to 1,000,000
TONs up to 150,000
TONs up to 250,000
Performances in C–C bond formation at 10-1 to 10-4 mol%
J.-C. Hierso, H. Doucet et al., Organometallics, 2003, 22, 4490.
J.-C. Hierso, V. V. Ivanov , H. Doucet et al., Org. Lett., 2004, 6, 3473.
J.-C. Hierso et al. Tetrahedron. 2005, 61,975.
H. Doucet, J.-C. Hierso, Angew. Chem. Int. Ed. 2007, 46, 834.
Heck and Sonogashira protocols: inspiring C–H functionalization
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Cl
Br
I
H
Aromatics molecular mass
MH =1
MCl=35
MI =127
MBr = 80
Mw = 78
Mw = 112
Mass loss
Mw = 157
Mw = 204
Mass loss percent
1.28 %
31.25 %
50.96 %
62.25 %
• Mass loss during coupling processes with benzene and halobenzenes
Csp2–Csp2 bond formation with heteroaromatics
see Adv. Synth. Catal. 2008, 350, 2183 and ref. therein
+ Pd
• Stoichiometric metallic waste is produced • Necessary preparation of organometallics for Suzuki, Stille, Negishi coupling
ClR1 Pd /Ligand +
Direct C–H functionalization of heteroaromatics for atom economy
Stabilizing polydentate ligands may help to this objective
that is not achieved under ligand-free conditions ?
8
9
Heteroaromatics functionalization as waste valorization
Furan derivatives from agriculture wastes as starting materials ?
10
Convergent synthesis towards high-value fine chemicals ?
High value convergent synthesis
N
CONHPh
FCO2H
OH OH
Atorvastatin cholesterol regulator
=> 12 billion US$ sales in 2008
Dantrolen : Muscle relaxant Amiphenazole
respiratory stimulant
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A 2nd generation of ferrocenylphosphines for C–H/C–Cl cross-coupling
S. Mom, J.-C. Hierso et al. Inorg. Chem. , 2011, 50, 11592. Sophal Mom (PhD ANR)
12 D. Roy, S. Mom, H. Doucet, J.-C. Hierso Angew. Chem. Int. Ed., 2010, 49, 6650.
X
CN
X = O (83%)X = S (90%)
X
CN
X = O (85%)X = S (17%)
X
C N
X = O (87%)X = S (52%)
S
CN
O
O
79 %
SC
C
52%
N
NX
O
X = O (72%)X = S (73%)
O
O
O60%
CNX
X = O (84%)X = S (90%)
O
X
O2N
X = O (74%)X = S (80%)X
F3C
X = O (73%)X = S (81%)
N
S
92%
CNN
S
83%O
N
S
62%O
N
77%O
O
N
C
90%
NO
N
63%
O
O
N
63%C N
ON
50% O
O
Direct arylation in -C2 (or C5) from activated chlorides
Functionalized thiophenes and furans
Functionalized pyrroles and thiazoles
D. Roy (PhD ANR)
13 D. Roy, S. Mom, J.-C. Hierso, H. Doucet et al. Chem.-Eur. J., 2011, 17, 6453.
O
O
O
72%
O
O 71%
N
S
94%
N O 60%S
CN92% O
O
O
68%
O
O
O
CN
93%
SCN
CN 93%
N
CN
O52%
SCN
90%
O
OH
86%
O
EtO
OEt
O
68%
Naphtalenes
Anthracenes
Biphenyls Ortho and di-ortho-functionalized arenes
Direct arylation in -C2 (or C5) from congested bromides
D. Roy, D. Lucas, J.-C. Hierso, H. Doucet et al. ACS Catalysis, 2012, 1033.
Isoxazoles
Pyrazoles
Indoles
Benzofurans
Steric effects and flexibility are
dominant over electronic effects
(ē donation is equivalent to PPh3)
Direct arylation in -C3 (ou C4) from activated chlorides
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15
C–O coupling of substituted phenols with heteroaryl chlorides
M. Platon, J.-C. Hierso et al. Adv. Synth. Catal. 2011, 353, 3403-3414.
98%
NO
99%
NO
NC
88%
NO OMe
95%N
NO
90%N
NO
O
61%N
S
87%
NO
iPr75%
NO
iPr
55%
NO
iPr
iPr98%
NO
NC
MeO
60%
NO
NH2
84%
NO
CEtO
O
98%
NO
NCF
90%
NO
92%
NO
OMe
NC 80%
NO
CEtO O 21%
NO
CEtO O
N
N
O
90%
Mélanie Platon (PhD)
tBu
Ph2P
PPh2
PPh2
tBu
PPh2
Fe
Pd
Br
Br
Fe
tBu
Ph2P
PPh2
PPh2
tBu
PPh2
Pd0
Electrochemicalreduction
Fe
tBu
Ph2P
PPh2
PPh2
tBu
PPh2
Pd0
Stabilization f romthe involvement
of the third phosphorus
Unstable speciesdetected in NMR
(low lif e-time)
35 ppm
23 ppm
34 ppm
- 20 ppm
tBu
Ph2P
PPh2
PPh2
tBu
PPh2
Fe
Pd
I
I
Oxidativeaddition
t1/2 = 130 ms
t1/2 = 30 s for [Pd0(PPh3)4] 200 times slower
t1/2 = 80 ms for “Pd0(PPh3)2” Stability gain x1,5
D. Evrard, D. Lucas, J.-C. Hierso, et al. Organometallics, 2008, 27, 2643.
Influence of polyphosphines on the reactivity of Pd(0)
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Oxydative addition (OA) of aryl halides
V. Zinovyeva, D. Lucas, J.-C. Hierso et al. Chem. Eur. J. , 2011, 17, 9901. 17
Influence of polyphosphines on the selectivity of OA
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Influence of polyphosphines on the reactivity of Pd(II)
Reductive elimination (RE) of heteroaromatic aryl ethers
M. Platon, M. Saeys, J.-C. Hierso et al. Adv. Synth. Catal. 2011, 353, 3403.
For the lowest energy pathway RE is 400-fold faster at 115 °C
(effective activation barrier is 19 kJ/mol lower than that for RE.TS1 pathway).
Iso.TS1-2
Iso.TS2-3
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Copper-phosphine chemistry for economic and fundamental concerns
Copper reserves : 5.5x108 t 25 years to 60 years left Price : 4-7 €/Kg
Palladium reserves : 8.0x104 t 300 years left Price : 6000 – 40000 €/Kg
• Copper catalysis (Ullmann, Click, etc.) is dominated by complexes having nitrogen an oxygen-containing ligands .
Phosphine are almost absent (HSAB theory): what about polyphosphines ?
• Fine mechanisms are poorly-known compared to palladium catalysis ( CuI/CuIII ??) could we get some help from 31P NMR ?
CuI/k3-tetra- and triphos
First Cu-polyphosphine adducts for Sonogashira coupling
M. Beaupérin, A. Job, J.-C. Hierso et al. Organometallics 2010, 29, 2815. 20
(1) concurrent palladium catalytic cycle for alkyne dimerization
I. J. S. Fairlamb et al., J. Org. Chem. 2005, 70, 703.
CuI-adducts only does not achieve Sonogashira reaction… …but may be are an inventive way to prevent diyne formation* !
(2) concurrent copper-dimers promoting alkyne dimerization
F. Diederich et al. Angew. Chem., Int. Ed. 2000, 39, 2632.
* Diyne formation promoted by O2 is the major concurrent reaction of alkynes arylation 21
A simple copper-diolefin for versatile arylation of pyrazole
V. Rampazzi, P. Le Gendre, J.-C. Hierso et al. ChemCatChem , 2012, DOI10.1002/cctc.201200368
[CuIPPh2(Cyhd)]4
(Cyclohepta-3,5-dienyl)diphenylphosphine
Molecularly-defined cubane precatalyst
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M. Taillefer et al., Angew. Chem. Int. Ed. 2009, 48, 333-336.
Arylation of nucleophiles with a butadienylphosphine
A large scope of (hetero)aromatic bromides coupled to pyrazoles
Pyridinyl
Pyrimidinyl
Furyl
Thienyl Thiazolyl
Aryl
The trap of aromatic chlorides: easy SNAr
V. Rampazzi, P. Le Gendre, J.-C. Hierso et al. ChemCatChem , 2012, DOI10.1002/cctc.201200368 23
Team ANR U. Dijon
J-C Hierso Dominique Lucas Philippe Meunier Régine Amardeil Charles Devillers
S. Mom Vero Zinovyeva
Special thanks and support
• Université de Bourgogne et Université de Rennes • CNRS – Institut de Chimie • ANR (Programme CP2D et Blanc - ANR Camelot) • RDR – GDR Chimie durable • Ministère des Affaires Etrangères et Programme Hubert Curien • Département de valorisation de l’IC-CNRS
Team ANR U. Rennes
Henri Doucet J. Roger D. Roy
Institut Universitaire de France Conseil régional de
Bourgogne 24
ANR Camelot (2009-2012): Main bibliography
S. Mom, J.-C. Hierso et al. Inorg. Chem., 2011, 50, 11592.
D. Roy, S. Mom, H. Doucet, J.-C. Hierso Angew. Chem. Int. Ed., 2010, 49, 6650.
D. Roy, S. Mom, J.-C. Hierso, H. Doucet et al. Chem. Eur. J., 2011, 17, 6453.
• Main topic : polyphosphines – C–H/C–Cl functionalization – palladium
• Second topic : phosphine ligands – copper catalysis
• Related topics : arylation reactions – catalysis in water and ionic liquids
D. Roy, S. Royer D. Lucas, J.-C. Hierso, H. Doucet et al. ACS Catalysis, 2012,1033.
V. Zinovyeva, D. Lucas, J.-C. Hierso et al. Chem. Eur. J., 2011, 17, 9901.
J. Roger, S. Mom, H. Doucet, J.-C Hierso ChemCatChem , 2010, 2, 296.
M. Platon, M. Saeys, J.-C. Hierso et al. Adv. Synth. Catal. 2011, 353, 3403.
S. Saleh, S. Mom, H. Doucet, J.-C Hierso et al. Synlett. 2011, 19, 2844.
V. Zinovyeva, D. Lucas, J.-C. Hierso et al. Adv. Funct. Mater. 2011, 21, 1064.
V. Rampazzi, P. Le Gendre, J.-C Hierso et al. ChemCatChem. 2012, DOI10.1002/cctc.201200368
M. Beaupérin, A. Job, J.-C. Hierso et al. Organometallics 2010, 29, 2815.
M. Platon, J.-C. Hierso et al. Chem. Soc. Rev. 2012, 41, 3929. 25
Commercially available
http://www.strem.com/catalog/ligands.php HiersoPHOS-1 à 5
HiersoPHOS-1
3 4
2
5
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