View
36
Download
0
Category
Tags:
Preview:
DESCRIPTION
Diaryliodonium Salts in Coupling Reactions. Sébastien R. Goudreau. Literature Meeting. November 9 th , 2009. Cross-Coupling: General Mechanism. Oxidative Addition Favored by Electron-Rich Palladium and Electron-Poor R group. Substitution (trans-metalation) - PowerPoint PPT Presentation
Citation preview
+catalyst
R I Ar Ar
X X
X
Sébastien R. Goudreau
Literature Meeting
Diaryliodonium Salts in Coupling Diaryliodonium Salts in Coupling ReactionsReactions
November 9th, 2009
2
LPd
LPdX
RLPd
Nu
R
Nu EE X
R XNu R
oxidativeaddition
reductiveelimination
substitution
N. Miyaura, A. Suzuki, Chem. Rev. 1995, 95, 2457-2483.
Cross-Coupling: General MechanismCross-Coupling: General Mechanism
Oxidative AdditionFavored by Electron-Rich Palladiumand Electron-Poor R group
Substitution (trans-metalation)Favored by Electron-Poor Palladiumand Electron-Rich Nu group
3
I
X
LPd
LPdX
RLPd
Nu
R
Nu EE X
R XNu R
oxidativeaddition
reductiveelimination
substitution
Cross-Coupling: General MechanismCross-Coupling: General Mechanism
X = I > OTf > Br >>> Cl
diaryliodonium salts
N. Miyaura, A. Suzuki, Chem. Rev. 1995, 95, 2457-2483.
106 faster then X = I
4P. J. Stang, V. V. Zhdankin, Chem. Rev. 1996, 96, 1123-1178. E. A. Merritt, B. Olofsson, Angew. Chem., Int. Ed. 2009, ASAP
ReactivityReactivity
5
I
X
NuI
X
NuM
M
I Nu
I
X
I
X MM I XM
+
P. J. Stang, V. V. Zhdankin, Chem. Rev. 1996, 96, 1123-1178. E. A. Merritt, B. Olofsson, Angew. Chem., Int. Ed. 2009, ASAP
ReactivityReactivity
6P. J. Stang, V. V. Zhdankin, Chem. Rev. 1996, 96, 1123-1178. E. A. Merritt, B. Olofsson, Angew. Chem., Int. Ed. 2009, ASAP
NucleophilesNucleophiles
7
Cross-Cross-CouplingCoupling
8
(Ph3P)2PdX
R
(Ph3P)2PdNu
R
Nu B
R XNu R
oxidativeaddition
reductiveelimination
substitution
Pd(PPh3)4
-2PPh3
Pd(PPh3)2
OH
OR2
OH
R2O B OH
OR2
OH
(Ph3P)2PdOR2
R
Nu BOH
OH
MOR2
M
M
MOR2
MX
B(OH)2 + I
Pd(PPh3)4
MOR2
X Y X Y
Suzuki Cross-Coupling ReactionSuzuki Cross-Coupling Reaction
N. Miyaura, A. Suzuki, Chem. Rev. 1995, 95, 2457-2483.
9
B(OH)2 + I
Pd(PPh3)4
DME, 80 °C
54%
aq. K2CO3
HO
HO
H
HO
+
39%
Ph B(OH)2 + I NO2 Ph NO2
Pd(PPh3)4 : 8h, 23%
acetone, 65 °C
85%
aq. K2CO3
Pd(OAc)2 : 45 min, 98%
N. Miyaura, A. Suzuki, Chem. Rev. 1995, 95, 2457-2483.
Suzuki Cross-Coupling ReactionSuzuki Cross-Coupling Reaction
Ph B(OH)2 +Br
O
Ph
OPd(PPh3)4
DME, 100 °C
CsF
85%
10
Suzuki Cross-Coupling ReactionSuzuki Cross-Coupling Reaction
S.-K. Kang, H.-W. Lee, S.-B. Jang, P.-S. Ho, J. Org. Chem. 1996, 61, 4720-4724.
Ph B(OH)2 + [Ph2I]BF4
High yield without Base !
11
(Ph3P)2PdPh
(Ph3P)2PdNu
Ph
Nu B
Nu Ph
oxidativeaddition
reductiveelimination
substitution
Pd(PPh3)4
-2PPh3
Pd(PPh3)2
OH
OR2
OH
R2O B OH
OR2
OH
(Ph3P)2PdOR2
Ph
Nu BOH
OH
MOR2
M
M
MOR2
MBF4
[Ph2I]BF4
PhI
BF4
Suzuki Cross-Coupling ReactionSuzuki Cross-Coupling Reaction
S.-K. Kang, H.-W. Lee, S.-B. Jang, P.-S. Ho, J. Org. Chem. 1996, 61, 4720-4724.
12
Suzuki Cross-Coupling ReactionSuzuki Cross-Coupling Reaction
S.-K. Kang, H.-W. Lee, S.-B. Jang, P.-S. Ho, J. Org. Chem. 1996, 61, 4720-4724.
(Ph3P)2PdPh
(Ph3P)2PdNu
Ph
Nu Ph
oxidativeaddition
reductiveelimination
substitution
Pd(PPh3)4
-2PPh3
Pd(PPh3)2
BOH
OHNu B
OH
OH
[Ph2I]BF4
PhI
BF4
BF4O
B
Nu
OH
H+
BHO OH
OB
Nu
OHH+ Nu2
13
Method A: Pd(PPh3)4 (0.2 mol %)
Method B: Pd(OAc)2 (0.2 mol %)
Ar B(OH)2 + RAr[R2I]BF4Na2CO3
DME/H2O (4:1)
Suzuki Cross-Coupling ReactionSuzuki Cross-Coupling Reaction
S.-K. Kang, H.-W. Lee, S.-B. Jang, P.-S. Ho, J. Org. Chem. 1996, 61, 4720-4724.
14
S.-K. Kang, T. Yamaguchi, T.-H. Kim, P.-S. Ho, J. Org. Chem. 1996, 61, 9082-9083.
Copper-Catalyzed “Suzuki-Type” ReactionCopper-Catalyzed “Suzuki-Type” Reaction
Reaction did not work with ArI
Boronic acids
15
ICuPh
ICuNu
Ph
Nu B
Nu Ph
oxidativeaddition
reductiveelimination
substitution
CuI
OH
OR2
OH
R2O B OH
OR2
OH
ICuOR2
Ph
Nu BOH
OH
MOR2
M
M
MOR2
MBF4
[Ph2I]BF4
PhI
BF4
Copper-Catalyzed “Suzuki-Type” ReactionCopper-Catalyzed “Suzuki-Type” Reaction
S.-K. Kang, T. Yamaguchi, T.-H. Kim, P.-S. Ho, J. Org. Chem. 1996, 61, 9082-9083.
16
Carbonylative Copper-Catalyzed “Suzuki-Type” ReactionCarbonylative Copper-Catalyzed “Suzuki-Type” Reaction
S.-K. Kang, T. Yamaguchi, T.-H. Kim, P.-S. Ho, J. Org. Chem. 1996, 61, 9082-9083.
S.-K. Kang, S.-W. Lee, M.-S. Kim, H.-S. Kwon, Synth. Commun. 2001, 31, 1721 - 1725.S.-K. Kang, H.-C. Ryu, J.-W. Kim, Synth. Commun. 2001, 31, 1021 - 1026.
J.-M. Becht, C. L. Drian, Org. Lett. 2008, 10, 3161-3164.
Diaryliodonium salts work in all cross coupling reactions !
17
Suzuki Cross-Coupling ReactionSuzuki Cross-Coupling Reaction
S.-K. Kang, H.-W. Lee, S.-B. Jang, P.-S. Ho, J. Org. Chem. 1996, 61, 4720-4724.
(Ph3P)2PdPh
(Ph3P)2PdNu
Ph
Nu Ph
oxidativeaddition
reductiveelimination
substitution
Pd(PPh3)4
-2PPh3
Pd(PPh3)2
BOH
OHNu B
OH
OH
[Ph2I]BF4
PhI
BF4
BF4O
B
Nu
OH
H+
BHO OH
OB
Nu
OHH+ Nu2
Fast oxydative addition
Electrophilic Palladium(II)
18
Pd Catalyzed C-H Pd Catalyzed C-H FunctionalizationFunctionalization
19
O. Daugulis, V. G. Zaitsev, Angew. Chem., Int. Ed. 2005, 44, 4046-4048.
+catalyst
H Ar Ar
Y Y
X
reductiveelimination
cyclo-palladation
ZR H
Z(AcO)2Pd
R H
ZPdRAcO
II
Pd(OAc)2
II
AcOH
ZPdRX
IV
R2
OAc
ZRR2
oxidativeaddition
R2X
AcOH
HX +
ZPd
R H II
reductiveelimination
cyclo-palladation
ZPdRAcO
II
ZRR2
oxidativeaddition
LnPdAr
PdLn
OAcAr
HX
AcOH+
OAc
ZR H
R X
AcOH
Cyclopalladation MechanismsCyclopalladation Mechanisms
20
O. Daugulis, V. G. Zaitsev, Angew. Chem., Int. Ed. 2005, 44, 4046-4048.
+catalyst
H Ar Ar
Y Y
X
(Ph3P)2PdX
R
R X
oxidativeaddition
reductiveelimination
Pd(PPh3)4
-2PPh3
Pd(PPh3)2
electrophilicpalladation
(Ph3P)2PdR
H
X
(Ph3P)2PdR
R
reductiveelimination
Pd(OAc)2
electrophilicpalladation
AcOPd H
AcO
AcOPd
R
AcOH
oxidativeaddition
PdRPh
IV
X
OAc
R X
AcOH
HX +
Electrophilic Palladation MechanismsElectrophilic Palladation Mechanisms
21
O. Daugulis, V. G. Zaitsev, Angew. Chem., Int. Ed. 2005, 44, 4046-4048.
reductiveelimination
cyclo-palladation
Pd(OAc)2
AcOH
oxidativeaddition
O
tBuHN
H
OHN
tBuOAc
OAcH
OHN
tBuOAc
AcOH
OHN
tBu Ar
OAc
[Ar2I]PF6
IVPF6
O
tBuHN
ArHPF6 +
reductiveelimination
cyclo-palladation
oxidativeaddition
R2X
LnPdAr
[Ar2I]PF6PdLn
HPF6
AcOH+
OAc
PhI +
OHN
tBuAr
OAcH
O
tBuHN
OHN
tBuAr
O
tBuHN
Ar+
ZaitsevZaitsev
22
O. Daugulis, V. G. Zaitsev, Angew. Chem., Int. Ed. 2005, 44, 4046-4048.
ZaitsevZaitsev
23
O. Daugulis, V. G. Zaitsev, Angew. Chem., Int. Ed. 2005, 44, 4046-4048.
Reaction faster with Ar-I containing electron-donating groups
Reaction is faster with anilides containing electron-donating groups
ZaitsevZaitsev
24
reductiveelimination
Pd(OAc)2
electrophilicpalladation
R
AcOH
oxidativeaddition
AcOH
+
[Ar2I]PF6
HPF6
PhI
PdAcO
NH
tBuOL
HN tBu
O
PdAcO H
AcO
NH
tBuOL
OHN
tBu Ar
OAc
IVPF6
LnPdAr
oxidativeaddition
reductiveelimination
PdLn
electrophilicpalladation
PdR H
X
R[Ar2I]PF6
PF6
HN tBu
O
NH
tBuOL
PdR
NH
tBuOL
HN
O
tBu
Mechanism ?Mechanism ?
O. Daugulis, V. G. Zaitsev, Angew. Chem., Int. Ed. 2005, 44, 4046-4048.
25
D. Kalyani, N. R. Deprez, L. V. Desai, M. S. Sanford, J. Am. Chem. Soc. 2005, 127, 7330-7331.
Substrate [Ph2I]BF4
(1.1-2.5 equiv)+
Pd(OAc)2 (5 mol %)
AcOH, benzene100 °C, 8-24 h
Product
SanfordSanford
26
D. Kalyani, N. R. Deprez, L. V. Desai, M. S. Sanford, J. Am. Chem. Soc. 2005, 127, 7330-7331.
SanfordSanford
Substrate [Ph2I]BF4
(1.1-2.5 equiv)+
Pd(OAc)2 (5 mol %)
AcOH, benzene100 °C, 8-24 h
Product
27
D. Kalyani, N. R. Deprez, L. V. Desai, M. S. Sanford, J. Am. Chem. Soc. 2005, 127, 7330-7331.
(1.1-1.3 equiv)
+Pd(OAc)2 (5 mol %)
100 °C, 12 hN AcOH
I ArN
Ar
SanfordSanford
28
D. Kalyani, N. R. Deprez, L. V. Desai, M. S. Sanford, J. Am. Chem. Soc. 2005, 127, 7330-7331.
(1.1-1.3 equiv)
+Pd(OAc)2 (5 mol %)
100 °C, 12 hN AcOH
I ArN
Ar
Reaction does not work with Ph-I or PhOTf
reductiveelimination
cyclo-palladation
Pd(OAc)2
AcOH
oxidativeaddition
O
tBuHN
H
OHN
tBuOAc
OAcH
OHN
tBuOAc
AcOH
OHN
tBu Ar
OAc
[Ar2I]PF6
IVPF6
O
tBuHN
ArHPF6 +
Mechanism ?Mechanism ?
reductiveelimination
Pd(OAc)2
electrophilicpalladation
R
AcOH
oxidativeaddition
AcOH
+
[Ar2I]PF6
HPF6
PhI
PdAcO
NH
tBuOL
HN tBu
O
PdAcO H
AcO
NH
tBuOL
OHN
tBu Ar
OAc
IVPF6
29
D. Kalyani, N. R. Deprez, L. V. Desai, M. S. Sanford, J. Am. Chem. Soc. 2005, 127, 7330-7331.
reductiveelimination
cyclo-palladation
Pd(OAc)2
AcOH
oxidativeaddition
O
tBuHN
H
OHN
tBuOAc
OAcH
OHN
tBuOAc
AcOH
OHN
tBu Ar
OAc
[Ar2I]PF6
IVPF6
O
tBuHN
ArHPF6 +
Mechanism ?Mechanism ?
reductiveelimination
Pd(OAc)2
electrophilicpalladation
R
AcOH
oxidativeaddition
AcOH
+
[Ar2I]PF6
HPF6
PhI
PdAcO
NH
tBuOL
HN tBu
O
PdAcO H
AcO
NH
tBuOL
OHN
tBu Ar
OAc
IVPF6
30
N. R. Deprez, D. Kalyani, A. Krause, M. S. Sanford, J. Am. Chem. Soc. 2006, 128, 4972-4973.
SanfordSanford
31
N. R. Deprez, D. Kalyani, A. Krause, M. S. Sanford, J. Am. Chem. Soc. 2006, 128, 4972-4973.
SanfordSanford
32
SanfordSanford
N. R. Deprez, D. Kalyani, A. Krause, M. S. Sanford, J. Am. Chem. Soc. 2006, 128, 4972-4973.
33
D. C. Powers, M. A. L. Geibel, J. E. M. N. Klein, T. Ritter, J. Am. Chem. Soc. 2009, ASAP.
RitterRitter
34
RitterRitter
D. C. Powers, M. A. L. Geibel, J. E. M. N. Klein, T. Ritter, J. Am. Chem. Soc. 2009, ASAP.
35
Cu Catalyzed C-H Cu Catalyzed C-H FunctionalizationFunctionalization
36
R. J. Phipps, N. P. Grimster, M. J. Gaunt, J. Am. Chem. Soc. 2008, 130, 8172-8174.
GauntGaunt
37
R. J. Phipps, N. P. Grimster, M. J. Gaunt, J. Am. Chem. Soc. 2008, 130, 8172-8174.
GauntGaunt
38
R. J. Phipps, N. P. Grimster, M. J. Gaunt, J. Am. Chem. Soc. 2008, 130, 8172-8174.
GauntGaunt
39
R. J. Phipps, N. P. Grimster, M. J. Gaunt, J. Am. Chem. Soc. 2008, 130, 8172-8174.
GauntGaunt
40
R. J. Phipps, N. P. Grimster, M. J. Gaunt, J. Am. Chem. Soc. 2008, 130, 8172-8174.
GauntGaunt
41
R. J. Phipps, N. P. Grimster, M. J. Gaunt, J. Am. Chem. Soc. 2008, 130, 8172-8174.
GauntGaunt
42
R. J. Phipps, M. J. Gaunt, Science 2009, 323, 1593-1597.
GauntGaunt
43
R. J. Phipps, M. J. Gaunt, Science 2009, 323, 1593-1597.
GauntGaunt
44
GauntGaunt
45
SynthesisSynthesis
46
M. Bielawski, B. Olofsson, Chem. Commun. 2007, 2521-2523.
SynthesisSynthesis
M. Bielawski, M. Zhu, B. Olofsson, Adv. Synth. Catal. 2007, 349, 2610-2618.
47
M. Bielawski, B. Olofsson, Chem. Commun. 2007, 2521-2523.
SynthesisSynthesis
M. Bielawski, M. Zhu, B. Olofsson, Adv. Synth. Catal. 2007, 349, 2610-2618.
48
SynthesisSynthesis
M. Zhu, N. Jalalian, B. Olofsson, Synlett 2008, 592-596.E. A. Merritt, J. Malmgren, F. J. Klinke, B. Olofsson, Synlett 2009, 2009, 2277-2280.
49
ConclusionConclusion
+catalyst
R I Ar Ar
X X
X
Diaryliodonium salts:
Cross-Coupling
Pd Catalyzed C-H Functionalization
Pd Catalyzed C-H Functionalization
Synthesis
50
ThanksThanks
Recommended