organo-metal cooperative catalysis ♦ 3rd year seminar tiffany piou supervisors: dr. luc neuville...
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Organo-metal cooperative catalysis
♦
3rd year seminar
Tiffany Piou
Supervisors: Dr. Luc Neuville and Prof. Jieping Zhu
25.01.12
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Transition metal catalysis
One of the most useful and powerful tool in organic chemistry.
Advantages:
- Chemoselectivity- Regioselectivity- Stereoselectivity- High yield- Reproducibility- Low catalyst loading
Examples of transition metal reactions:
- Cross-coupling - Hydroformylation - Alkene and alkyne metathesis- Hydrogenation- Cyclopropanation - Hydroamination- Hydroesterification- Hydrocarboxylation- Pauson-Khand reaction- Isomerisation of olefins- Hydrocyanation
Transition Metals for Organic Synthesis: Building Blocks and Fine Chemicals (Eds.: M. Beller, C. Bolm), Wiley-VCH, Weinheim, 2nd ed., 2004, vol. 1 and 2.
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Organocatalysis
Major topic in organic chemistry
Access to enantiomerically enriched molecules
Explosion of new organocatalysts
NH O
OP
O
OH
NH
NO
tBu
Ar
Ar
Ph Ph
OTMS
N
MeO
HON
S
NH
NH
R2
R1
N NR3 R2
NH
CO2H
Main advantages:
- Not expensive- Easily accessible- Stable to air and moisture
Enantioselective Organocatalysis: Reactions and Experimental Procedure (Ed,: P. I. Dalko), Wiley-VCH, Weinheim, 2007.
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Cooperation between transition metal and organocatalyst
Concept introduced by Krische in 2003.
R
OOCO2Me PBu3 (100 mol%),
Pd(PPh3)3 (1 mol%)
tBuOH, 60°C.R
O
64-92%n
n
R
O
nBu3P
PdII
PBu3
Pd0
CO2OCH3
R
O
Bu3P
HPd0
OCH3
Pd0
PBu3
CH3OH
Combine Morita-Baylis-Hillman type reaction and Tsuji-Trost reaction
Use of “non classical” electrophilic partner
Open new perspectives
B. G. Jellerichs, J.-R. Kong, M. J. Krische J. Am. Chem. Soc. 2003, 125, 7758-7759.
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Cooperation between transition metal and organocatalyst
Metal +
Organocatalyst
Cooperative catalysis
Unprecedented transformations not currently possible with the transition metal or the organocatalyst alone.
New tool in organic chemistry
Problem: compatibility?
C. Zhong, X. Shi, Eur. J. Org. Chem. 2010, 2999-3025.Z. Shao, H. Zhang, Chem. Soc. Rev. 2009, 38, 2745-2755.
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ACatalyst 1
+Catalyst 2
BA Catalyst 1
B
CCatalyst 2
Two different types of cooperation
The two catalysts operate simultaneously
The two catalysts operateSuccessively in a “one pot” fashion
C. Zhong, X. Shi, Eur. J. Org. Chem. 2010, 2999-3025.Z. Shao, H. Zhang, Chem. Soc. Rev. 2009, 38, 2745-2755.
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ACatalyst 1
+Catalyst 2
BA Catalyst 1
B
CCatalyst 2
Two different types of cooperation
The two catalysts operate simultaneously
The two catalysts operateSuccessively in a “one pot” fashion
C. Zhong, X. Shi, Eur. J. Org. Chem. 2010, 2999-3025.Z. Shao, H. Zhang, Chem. Soc. Rev. 2009, 38, 2745-2755.
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Cooperative Reactions:
Transition Metal+
Organocatalyst
Aminocatalysis
Brönsted acid/base
Lewis Base
Bifunctional catalystNHC organocatalyst
C. Zhong, X. Shi, Eur. J. Org. Chem. 2010, 2999-3025.Z. Shao, H. Zhang, Chem. Soc. Rev. 2009, 38, 2745-2755.
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Transition metal with aminocatalysis
N
R1
R2
E R1
N
R2
Nu
Enamine catalysis Iminium catalysis
LUMO loweringHOMO raising
Functionnalization of carbonyl compounds
Pioneering work by Barbas, List and MacMillan
Amine activations are the most studied organocatalytic system
One of the most popular strategies in cooperative catalysis
S. Mukherjee, J. W. Yang, S. Hoffmann, B. List, Chem. Rev. 2007, 107, 5471-5569.
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First example, Cordova et al. in 2006,
Intermolecular α-allylation
H
N
R
RM
AcO R3 R2
O
R1
Pd(PPh3)4 (5 mol%)
(10-30 mol%) DMSO, rt.N
H
R2
O
R1
R3
up to 95% yield
Breit et al. in 2009,
HOR3
R1
O
R2
Pd(-allyl)Cl2 (2.5 mol%)
XantPhos (5.0 mol%)
(DL)-proline (30 mol%)
DMSO, 70 °C, 20 h
O
R1
R2
R3
NH
HOOC
O
H
H O
O
N
H2O
PdL
L
Pd
LLNO2C
tight ion pair
No stereoselectivity
I. Ibrahem, A. Cordova, Angew. Chem. Int. Ed. 2006, 45, 1952-1956.I. Usui, S. Schmidt, B. Breit, Org. Lett. 2009, 11, 1453-1459.
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Saicic et al. in 2007,
Intramolecular α-allylation
H
N
R
RM
O
H
Br
EtO2C CO2Et
(R)-(BINAP)Pd (7 mol%),pyrrolidine,
Et3N, THF, -20 °C
HO
EtO2C CO2Et
y = 40%, 91% ee
O
H
OP(O)(OEt)2
EtO2C CO2Et
(R)-(Ph-MeOBIPHEP)Pd (10 mol%),pyrrolidine,
Et3N, THF, -20 °C
HO
EtO2C CO2Et
y = 76%dr = 7.4:1, 98% ee
MeO
MeO
PPh2
PPh2
(R)-(Ph-MeOBIPHEP)
Chiral amine catalysts tested failed
2009,
F. Bihelovic, R. Matovic, B. Vulvovic, R. N. Saicic, Org. Lett. 2007, 9, 5063-5066.B. Vulvovic, F. Bihelovic, R. Matovic, R. N. Saicic, Tetrahedron 2009, 65, 10485-10494.
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Enamine addition to activated alkyneH
N
RR
M
H
O
R1
R2NH2
O
R3
R4
Proline (10 mol%)AgOTf (10 mol%)
EtOH, 50-60 °CNH
R4
O
R3
R1
H
N
R1
R2
Ag
N
R3
R4
HO2C
up to 95%
Multicomponent reaction developed by Wu’s group in 2007,
O
R1
R2
EWG EWG
R3
pyrrolidine (20 mol%)ps-BEMP (10 mol%)
Cu(OTf)2 (5 mol%)PPh3 (20 mol%)
MeOH, rt
R1
O R3
R2EWG
EWG
N
R1
R2
EWG EWG
R3
N
R1
R2
[Cu]
EWG EWG
71-82%
Tandem reaction published by Dixon’s,
Q. Ding, J. Wu, Org. Lett. 2007, 9, 4959-4962.T. Yang, A. Ferrali, L. Campbell, D. J. Dixon, Chem. Commun. 2008, 2923-2925.
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Enamine induced enantioselective cooperative reaction
R1
OH
R2
O
O
R2
R1
O
R2
R1
93% yieldsyn/anti 2.0-3.0:1
up to 99% ee
chiral amine (5 mol%)[Ru] (5 mol%)
NH4BF4 (10 mol%)toluene, rt
NH
ArAr
OTMS
Ar = 3,5-(CF3)2C6H3
Ru RuS
S
Cp*Cp*
MeMe
Cl Cl
[Ru]
R1 H
R1
OH
[Ru]
H
OH
R1
vinylidene complex
-H2O
N
R2
[Ru]
N
[Ru]
[Ru]
H
OO
R2
R1
-H2O
[Ru]
R1 H
N
OSiMe3
ArAr
minor
[Ru]
H R1
N
OSiMe3
ArAr
major
Nishibayashi et al in 2010,
M. Ikeda, Y. Miyake, Y. Nishibayashi, Angew. Chem. Int. Ed. 2010, 49, 7289-7293.
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Enamine catalysis with SOMO photoredox catalysis
Br FGH
O
Y
fluorescent lightMacMillan's catalyst
Ru(bpy)2Cl2, 2,6-lutidineDMF, rt
H
O
Y
R
FG
up to 92% yieldup to 99% ee
R
NH
NOMe
Me
tBu
MacMillan's catalyst
[Ru]2+
photoredox catalyst
[Ru]2+*
h
[Ru]+
oxidant
SET
FG Br
FG
.
Brreductant
N
NOMe
Me
tBu
R
N
NOMe
Me
tBu
FG
R
SET
FG
N
NOMe
Me
tBu
FG
R
NH
NOMe
Me
tBu
O
HR
O
H FG
R
A. Nicewicz, D. W. C. MacMillan, Science 2008, 322, 60-77.
SET = single electron transfer
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Cooperative Reactions:
Transition Metal+
Organocatalyst
Aminocatalysis
Brönsted acid/base
Lewis Base
Bifunctional catalystNHC organocatalyst
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Chiral Brönsted-acid/base with metal activated substrates
Chiral Brönsted acid/base catalyst: a powerful strategy.
In combination with transition-metal, 3 approaches:
OP
O
OR* OR*
H
Nu
E+
[M]
Asymmetric Counter Anion Directed Catalysis (ACDC)
R
X
H
H X*
[M] Nu
Chiral Brönsted Acid Activation
R3NH
Nu
[M] E
Chiral Brönsted BaseInduced Nucleophiles
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Chiral Brönsted-acid/base with metal activated substrates
Chiral Brönsted acid/base catalyst: a powerful strategy.
In combination with transition-metal, 3 approaches:
OP
O
OR* OR*
H
Nu
E+
[M]
Asymmetric Counter Anion Directed Catalysis (ACDC)
R
X
H
H X*
[M] Nu
Chiral Brönsted Acid Activation
R3NH
Nu
[M] E
Chiral Brönsted BaseInduced Nucleophiles
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Asymmetric Counter-Anion-directed catalysis Strategy (ACDC)
First example proposed by Toste et al,
OP
O
OR* OR*
H
Nu
E+
[M]
NHSO2Mes
R3 R4
R1
R2
PhMe2OAuCl (5 mol%)Ag/(R)-TRIP (5 mol%)
PhH, 23 °C, 48 h
NR1
R2
SO2MesH
R3R4
up to 97% yieldup to 98% ee
R3 R4
R1
R2
OH
R5 R6
PhMe2OAuCl (5 mol%)Ag/(R)-TRIP (5 mol%)
PhH, 23 °C, 48 h
OR1
R2
H
R3R4
R5
R6
up to 91% yieldup to 99% ee
O
OP
O
OAg
iPr
iPriPr
iPr
iPr iPr
Ag/(R)-TRIP
G. L. Hamiltion, E. J. Kang, M. Mba, F. D. Toste, Science 2007, 317, 496-499.
[LAuX] Ag Y [LAu] Y AgX
chiral ion pair
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Enantioselective α-allylation of aldehyde via ACDC strategy O
PO
OR* OR*
H
Nu
E+
[M]
HO
R3
R4R1 CHO
R2
Pd(PPh3)4 (1.5 mol%)(S)-TRIP (3.0 mol%)
(40 mol%)
MS 5A, toluene, 40 °Cthen HCl (2N)
R1 CHO
R2
R3
R4
Ph NH2
Ph
97% yielder up to 99.8:0.2
O
POR*HO
OR*
OH
HO
P
O
OR*OR*
OH
-H2OPd
Ph3P PPh3
O
POR*
OR*
O
O
Pd
PO
OR* OR*
HN Ph
Ph
R2
R1 H
Pd(0)
Ph
NH
PhPh
NH2Ph
Ph
NH
H
PhO
H
Ph -H2O
+H2O
Ph
CHO
G. Jiang, B. List, Angew. Chem. Int. Ed. 2011, 50, 9471-9474.
List et al.,
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Chiral Brönsted-acid/base with metal activated substrates
Chiral Brönsted acid/base catalyst: a powerful strategy.
In combination with transition-metal, 3 approaches:
OP
O
OR* OR*
H
Nu
E+
[M]
Asymmetric Counter Anion Directed Catalysis (ACDC)
R
X
H
H X*
[M] Nu
Chiral Brönsted Acid Activation
R3NH
Nu
[M] E
Chiral Brönsted BaseInduced Nucleophiles
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R
X
H
H X*
[M] Nu
Chiral Brönsted acid activation
Asymmetric alkynylation of α-imino esters proposed by Chan et al.:
H CO2Et
NPMP
Ph
Cu(OTf)2 0.5 C6H6
L1 (10 mol%)
DCM, 10 h Ph
CO2Et
NHPMP
up to 92% yieldup to 91% ee
H CO2Et
NPMP
Ar
Cu(OTf)2 0.5 C6H6
L2 (10 mol%)
DCM, 10 h Ar
CO2Et
NHPMP
up to 86% yieldup to 74% ee
N
ON
N
O
PhN
ON
N
O
Ph
L1
L2
Limited scope!
J.-X. Ji, J. Wu, A. S. C. Chan, Proc. Natl. Acad. Sci. USA 2005, 102, 11196-11200.
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R
X
H
H X*
[M] Nu
Chiral Brönsted acid activation: sp carbon nucleophile
H CO2Et
NPMP
R
R
CO2Et
NHPMP
up to 90% yieldup to 92% ee
cat. 1 (10 mol%)AgOAc (5 mol%)
toluene, rt, 10-12 h
O
OP
O
OH
Ar
Ar
Ar
1H CO2Et
NPMP
R'[Ag]OR*
P
O
OR*O
H
H R2
NR1
R
CuPF6 (2.5 mol%), P(o-tolyl)3Boc-proline (10 %mol)
DCM, 0°C, 72 hR2
NH
R3
R1
H R2
NR1
HO
O
NBoc
up to 92% yieldup to 99% ee
Rueping et al. 2007,
- Inexpensive catalyst- Large scope- Excellent ee
Arndtsen et al.,
M. Rueping, A. P. Antonchick, C. Brinkmann, Angew. Chem. Int. Ed. 2007, 46, 6903-6906.Y. Lu, T. C. Johnstone, B. A. Arnsdtsen, J. Am. Chem. Soc. 2009, 131, 11284-11285.
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Chiral Brönsted acid activation: Rh mediated-carbene nucleophile
R
X
H
H X*
[M] NuN2
Ar1 CO2R1R2OH
H
N
Ar3
Ar2 Rh2(OAc)4 (2 mol%)cat. 1 (2 mol%)
DCM, -20 °C Ar3
Ar1
NHAr2
R2OR1O2C
OO
PO
OH
Ar
Ar
Ar
cat. 1
RhLn
N2
Ar1 CO2R1
RhLn
Ar1 CO2R1
OR2H
Ar1 CO2R1
RhLn
OR2H
Ar1 CO2R1
H
N
Ar3
Ar2 H
NAr2
Ar3
O
PHO OR*
OR*
OP
O
OR*OR*
N
Ar3H
H
OP
O
R*O OR*
HO
R2
CO2R1Ar1
Ar3
Ar1
NHAr2
R2OR1O2C
O
PHO OR*
OR*
up to 98% yieldup to >99:1 drup to >99% ee
W.-H. Hu, X.-F. Xu, J. Zhou, W.-J. Liu, H.X. Huang, J. Hu, L. P. Yang, L.-Z. Gong, J. Am. Chem. Soc. 2008, 130, 7782-7783.
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Enantioselective hydrogenation of imine R
X
H
H X*
[M] Nu
R1
NPMP
R1 = aryl, alkyl.
S-TRIP (1 mol%), [Fe] (5 mol%)
50 bar H2, 65 °C, toluene, 24 h
R1
HNPMP
OCFe
OCH
TMS
TMSOH
Knölker's complex
R1
NPMP
P
OR*R*O
O
OH
R1
NPMPH
P
OR*R*O
O
O
[FeH2]
[Fe]
H2
R1
HNPMP
up to 96% yieldup to 98% ee
An alternative to the Hantzsch dihydropyridine
Beller’s group in 2011,
S. Zhou, S. Fleisher, K. Junge, M. Beller, Angew. Chem. Int. Ed. 2011, 50, 5120-5124.
25
Chiral Brönsted-acid/base with metal activated substrates
Chiral Brönsted acid/base catalyst: a powerful strategy.
In combination with transition-metal, 3 approaches:
OP
O
OR* OR*
H
Nu
E+
[M]
Asymmetric Counter Anion Directed Catalysis (ACDC)
R
X
H
H X*
[M] Nu
Chiral Brönsted Acid Activation
R3NH
Nu
[M] E
Chiral Brönsted BaseInduced Nucleophiles
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Me
NO2
CO2Et
NPMP
CO2Et
quinine (20 mol%)(R)-Ph-BOX-Cu(OTf)2 (20 mol%)
DCMMe HO2N
tBuO2C
NHPMP
CO2Et
N
MeO
NHO
O
N N
O
Ph PhCu
quinine
(R)-Ph-BOX-Cu(OTf)2
Me
NO2
CO2Et
NR1
R2
R3
H N
H
OEt
O
PMP CuH2N NH2
*
yield 90%dr 14:1ee 98%
R3NH
Nu
[M] E
Chiral Brönsted base and transition-metal Lewis acid
Enantioselective aza-Henry reaction,
K. R. Knudsen, K. A. Jorgensen, Org. Biomol. Chem. 2005, 3, 1362-1364.
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O
R1
O
R2
cat.1 (20 mol%)CuOTf 0.5 C6H6 (5 mol%)
DCM, rt, 1-4 days
O
R1
O
R2
up to 98% yieldup to 93% ee
N
NH
NHO
F3C CF3
N
cat. 1
Bronsted/Lewis base
hydrogen donor
2 distinct roles: - deprotonation of the enolate - ligand for copper
O
Ph
O
CO2Et
D
Ph
ODCu
L
conditions
O
Ph
DCuL
EtO2C
EtO2C
HO
Ph
D
EtO2C
Chiral Brönsted base and transition-metal Lewis acid R3NH
Nu
[M] EEnantioselective Conia-ene reaction
T. Yang, A. Ferrali, F. Sladojevich, L. Campbell, D. J. Dixon, J. Am. Chem. Soc. 2009, 131, 9140-9141.
28
Cooperative Reactions:
Transition Metal+
Organocatalyst
Aminocatalysis
Brönsted acid/base
Lewis Base
Bifunctional catalystNHC organocatalyst
29
Organic Lewis base with transition-metal activated electrophiles
Few examples probably because of compatibility problems
R
OOCO2Me PBu3 (100 mol%),
Pd(PPh3)3 (1 mol%)
tBuOH, 60°C.R
O
64-92%n
n
EWG
LB = PR3, NR3.
LB
EWG
LB
E [M]
Activation mode of Lewis base
B. G. Jellerichs, J.-R. Kong, M. J. Krische J. Am. Chem. Soc. 2003, 125, 7758-7759.
Krische in 2003,
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Organic Lewis base catalysed tandem reaction
CHO
R2
R3NH2
O
R4
AgOTf (10 mol%)PPh3 (20 mol%)
THF, 70 °C NR3
O
R4
R1
R1 R2
H2O
R2
R1N
R3[Ag] N
R3
[Ag]
R2R1
NR3
[Ag]
R2R1
PPh3
O
R4
PPh3
[Ag]
PPh3
O
R4H
AgOTfPPh3
45-70% yield
Wu et al. reported a 3 components reaction,
S. Ye, J. Wu, Tetrahedron Lett. 2009, 50, 6273-6275.
31
Cooperative Reactions:
Transition Metal+
Organocatalyst
Aminocatalysis
Brönsted acid/base
Lewis Base
Bifunctional catalystNHC organocatalyst
32
Bifunctional catalyst
Bifunctional catalyst
OrganocatalystMetal Ligand
New generation of catalyst
New strategy for cooperative catalysis
Enhance the compatibility between the metal and the organocatalyst
33
Bifunctional organocatalyst in cooperation with transition metal
Jun and co-workers,
Ar H
O
Ph
Rh(PPh3)3Cl (5 mol%)2-amino-3-picoline (20 mol%)
aniline (60 mol%)benzoic acid (6 mol%)
toluene, 150 °C, 24 hAr
O
R
up to 98%
C.-H. Jun, H. Lee, H. Lee, J.-B. Hong, Angew. Chem. Int. Ed. 2000, 39, 3070-3072.
NH2NMetal ligand
Organocatalyst
Ar H
O
Ar H
N N
NH2N
Ar
N N
RhL
LH
ClAr
N N
RhL
HCl
Ph
Ar
N N
RhLCl
R
Ar
N N
RRh(PPh3)3Cl
Ar
O
R
34
Bifunctional organocatalyst in cooperation with transition metal
O
R3R2
R1CHO
Cu(SbF6)2 (20 mol%)L1 (20 mol%)
THF, rt, 24-72 h
O
R3R2
R1
OH
NHN NH
O
HN
O
NHBoc
NHN NH
O
N
O
NHBoc
Cu
O
H R1
NHN NH
O
N
O
NHBoc
Cu
O
R1 H
disfavoredfavored
Tridentate ligand
organocatalystup to 96% yield
up to 99:1 drup to 99% ee
Maximize the compatibility between the Lewis base and Lewis acid
Wang et al,
Z. Xu, P. Daka, I. Budik, H. Wang, F. Q. Bai, H.-X. Zhang, Eur. J. Org. Chem. 2009, 4581-4585.
35
Cooperative Reactions:
Transition Metal+
Organocatalyst
Aminocatalysis
Brönsted acid/base
Lewis Base
Bifunctional catalystNHC organocatalyst
36
R H
O
N N ArAr
R
O
NHC-mediated reactions
R H
O conjugate umpolung
N N ArAr
R
OH
N
NAr
Ar
extended Breslow intermediate
R
OH
N
NAr
Ar
Homoenolate
R
OH
N
NAr
ArE
E
Tautomerisation
R
O
N
NAr
ArE
NuR
O
Nu
E
Bode and Glorius in 2004,
S. Sohn, E. L. Rosen, J. W. Bode, J. Am. Chem. Soc. 2004, 126, 14370-14371.C. Burstein, F. Glorius, Angew. Chem. Int. Ed. 2004, 43, 6205-6208.V. Nair, R. S. Menon, A. T. Biju, C. R. Sinu, R. R. Paul, A. Josea, V. Sreekumarc, Chem. Soc. Rev. 2011, 40, 5336-5346.
Tool to develop enantioselective tandem reaction
Application in cooperative catalysis, but compatibility?
37
NHC-catalysed cooperative reaction
Scheidt et al. in 2011,
R1
O
H
NHC catalyst (20 mol%)Ti(OiPr)4 (5 equiv.)
DBU (40 mol%)iPrOH, THF, 23 °C
R2
O
O
OMe
R1R2
OiPr
O
OiPrO
HO
H
52-85% yield20:1 dr
91-99% ee
R2
O
N N
N
Ar
O
H
HR1
OO
MeOC-C bondformation
(iPrO)nTi
R2
O
N N
N
Ar
O
H
HR1
OO
MeO
(iPrO)nTi
R2
O
N N
N
Ar
O
H
HR1
OO
MeO
(iPrO)nTi
protonation/tautomerization/
aldol
block the front faceof NHC-enal
The Lewis acid coordinate and activate the α-ketoester
New class of electrophiles for NHC-catalysed annulation
D. T. Cohen, B. Cardinal-David, K. A. Scheidt, Angew. Chem. Int. Ed. 2011, 50, 1678-1682