c-c bond formation through catalytic functionalization of ... · c-c bond formation through...
TRANSCRIPT
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C-C Bond Formation through Catalytic Functionalization of
sp3 C-H Bonds
Min XieOtc. 17, 2006
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Methods of sp3C-H Funtionalization
1. Oxidative insertion of transition metals:
2. Metal catalyzed dehydrogenation by oxidants
3. Lewis acids catalyzed H shift
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Why is sp3C-H Activation not Easy?
Bergman, Hoff, Polyhedron 1988,7,1429
sp3 C-M complexes are generally less stable.
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Oxidative Addition of Transition Metal into sp3C-H
M = Ti(IV),Zr(IV),Nb(V),Ta(V),W(VI)
Nugent,Organometallics,1983,2,161
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Chelation-assited Activation of sp3C-H
Bruce, ACIE, 1977,2,7
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sp3C-H Activation by Ru Catalyst
Jun,Chem.Comm.,1998,1405
95%
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Jun,Chem.Comm.,1998,1405
sp3C-H Activation by Ru(0) catalyst
Only 1-2% GC yield.
12
13+
15
16
Ru3(CO)12 (20 mol%)
PhMe, 130oC, 1.2h
39% (GC)
70%
12
14+
15
17
26%
60%
reactivity: 15 < 16 < 17
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Murai,JACS,2001,123,10935
Ru Catalyzed Coupling Reactions of C-H
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Murai,JACS,2001,123,10935
No reaction.
Ru Catalyzed Coupling Reactions of C-H
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Ru Activation of sp3C-H in Cyclic Amines
Murai,JACS,2001,123,1093592% (54/46)
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Ru Activation of sp3C-H in Acyclic Amines
Murai,JACS,2001,123,10935
CO not employed.Otherwise carbonylation at N-H bond.
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Ru Catalyzed Coupling Reactions of Alkenes
CN
n-BuO
R
a Reaction conditions: 1a (1 mmol), alkene (10 mmol), Ru3(CO)12 (0.08 mmol), in 2-propanol (2 mL) at 140 °C in a 10 mL stainless vial.b Isolated yields based on 1a. c The numbers in parentheses are the stereoisomeric ratios.
Fail to react.
Murai,JACS,2001,123,10935
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Proposed Mechanism
N
N Ru
N
NRu
N
N Ru HN
N RuRR
- RuN
N
N
N RuN
N Ru H
N
NRu
RR
N
NRuH
Murai,JACS,2001,123,10935
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N
N Ru H
H
N
N Ru- H2
OHO
Murai,JACS,2001,123,10935
Cleavage of C-H is not that difficult.
Solvent Effect
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Rh Catalyzed Carbonylation at sp3 C-H
Murai,JACS, 2000, 122, 12882
[RhCl(cod)2]2 is superior to [RhCl(CO)2]2 and Rh4(CO)12.
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Nalkyl
N N
N
N
N
N
N
HN
N
Ph N
N N
All failed.
Substrate Scope
Murai,JACS, 2000, 122, 12882
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Proposed Mechanism
Murai,JACS, 2000, 122, 12882
N
N Rh
N
NRh
N
N Rh HN
N Ru - Rh
N
N
N
N RhN
N Rh H
N
NRhH
CO
N
N RuO
O
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Rh Catalyzed Carbonylation of Piperazines
N
MeN
N
N
MeN
N
N
MeN
NO
N
MeN
NO
N
MeN
NO
Path a
Path b
?Murai,Organometallics,1997, 16, 3615
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Possible Intermediate
2-Pyridyl is essential for carbonylation, but not for dehydrogenation.
N
MeN
N
Hexene does not effect dehydrogenation.
Murai,Organometallics,1997, 16, 3615
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Substituent Effects
NPy
N
O
PyNPy
O
No reaction.
Murai,Organometallics,1997, 16, 3615
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Site Selectivity
Murai,Organometallics,1997, 16, 3615
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Proposed Mechanism
N
MeN
N
RhN
MeN
NRh H
H2C CH2
N
MeN
NRh Et
- C2H6
- RhN
MeN
N
Rh N
MeN
NRh H
H2C CH2
N
MeN
NRh Et
N
MeN
NRh
COON
MeN
N
- Rh
O
N
MeN
NRh
Not detected by GC.
- C2H6 1,3 H-shift
Murai,Organometallics,1997, 16, 3615
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C-H Activation Directed by N-Acyl Group
Murai, TL, 1997, 38, 7565
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C-H Activation Directed by N-Acyl Group
Possible mechanism for the formation of 11?
Murai, TL, 1997, 38, 7565
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C-H Activation Directed by N-Acyl Group
Possible mechanism for the formation of 11?
Murai, TL, 1997, 38, 7565
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C-H Activation Adjacent to Amides
N
O
1. Oxidative addition into C-H2. Intramolecular olefin insertion into Rh-H
1.β-hydride elimination2. Reductive eliminationRh
Sames, JACS, 2004, 126, 6556
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Brookhart ,JACS. 1999, 121, 4385
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Sames, JACS, 2004, 126, 6556
Ir Catalyzed Cyclization of Alkene-Amides
Known for catalytic transerdehydrogenation of alkanes.
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Active Intermediate
Isolated as solid.
[Ir(COE)2Cl]2 +
O
Ntoluene
50 oC
20 equiv.
IPr (2 equiv.)
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Possible Mechanism
IrOCl
IPrN
N
O
IrH IPr
ClC-H activation
C-C formation
N
O
Ir (Cl)IPrHN
O
Ir (Cl)IPrH2
β-hydride elimination
R
R
N
O
N
O
Sames, JACS, 2004, 126, 6556
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Sames, JACS, 2004, 126, 6556, SI
Alternative Mechanism: Dehydrogenation Followed by sp2 C-H Activation?
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FG Compatibility and Regioselectivity
Sames, JACS, 2004, 126, 6556, SI
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Funtionalyzation of C-H through Metal-oxo Species
Murahashi, ACIE, 1995,34,2443
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Ru Catalyzed Oxidative Cyanation of 3o AminesWith H2O2
Muraihashi,ACIE, 2005,44,6931
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Proposed Mechanism
Muraihashi,ACIE, 2005,44,6931
ρ value = -3.61
Cationic intermediate
KIE for N,N-dimethylaniline: intra 4.1 inter 3.7
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Areobic Oxidative Cyanation of 3o Amines
Muraihashi,JACS, 2003,125,15312
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Mechanistic Studies
NMeOMe
CD3
NMeMe
CD3
NMe
CD3
NBrMe
CD3
4.2
3.1
2.4
1.1
ρ value = -3.35
kH/kD
Muraihashi,JACS, 2003,125,15312
1 mol of O2 consumed 2 mol aniline.
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Cu Catalyzed Oxidative Alkynylation of C-H
Li, JACS, 2004,126,11810
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Li, JACS, 2004,126,11810
Substrate Scope
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Cu Catalyzed Asymmetric Alkynylation of C-H
Li, OL, 2004,6,4997
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Li, JACS, 2005,127,3672
Cu Catalyzed Nitro-Mannich Type Reaction
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Cu Catalyzed Coupling of Malonate and Tetrahydroquinoline
Li, PNAS, 2006,103, 8928
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Cu Catalyzed Aza–Baylis–Hillman type Reaction
Li, PNAS, 2006,103, 8928
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Cu Catalyzed Indolation
Li, JACS, 2005,127, 6968
1.3
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Proposed General Mechanism for Cu Catalyzed Cross-dehydrogenative Coupling Reactions
Li, PNAS, 2006,103, 8928
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Potential problem: β hydride elinination
Can 1,5-hydride shift take place?
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BF3 Et2O (2.0 equiv.)
DCM, reflux, 24h
76%
instead of
1,5 Hydride Shift in Pyrimidinone
Noguchi, JCS, Perkin Trans.1, 1998, 3327
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Sames, JACS, 2005, 127, 12180
Lewis Acid Catalyzed 1,5 Hydride Shift/Cyclizaiton
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Substrate Scope
Sames, JACS, 2005, 127, 12180
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Sames, OL, 2005, 7, 5429
Lewis Acid CatalyzedLewis Acid Catalyzed Cyclizaiton of Aldehydes
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Isotop Labeling and Cross-over Experiment
Sames, OL, 2005, 7, 5429
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Evidence for 1,5-Hydride Shift
Sames, OL, 2005, 7, 5429