Upload
anastasia-hall
View
282
Download
1
Embed Size (px)
Citation preview
Outline:
1. Introduction
2. Oxidative coupling
3. Nucleophilic Addition
4. Other Reactions
5. Conclusion
2
1. Introduction
3
Rh(I)/ ( III) Direct C-H Funtionalization
R BOH
OH
X BOH
OH
R Rh(I)Aldol-typeMannich-type1,4- addition
Hydrogenation
H2
C-X, C-O CleavageC-N, C-C CleavageIsomerization Yn-En
2. Oxidative Coupling
DG =
See: F. Glorius, J. A. Ellman, Sukbok Chang,T. Satoh, M. Miura Z.-J. Shi, X.-W. Li, T. Rovis, N. Cramer
N
R1
R2
O
R1
O
NR1R2
N
R1
OR2
O
OR1N
X HN R1
O
DG
H
Rh(III) DG
Rh(III)
RDG
R
Rh(III)
H
DG
R
elimination
Rh(I)[OX]
base
HXBase
electrophilicdeprotonation
Oxidizing DG
4
Heck Type
Arylation
Double C-Hactivation
F.Glorious, Angew. Chem. Int. Ed. 2012, 51, 2247
M. Miura, Angew. Chem. Int. Ed. 2012, 51, 5359
2. Oxidative Coupling
DG
H
Rh(III) DG
Rh(III)
DG
Rh(III)
DG
Rh(I)X
X X
[OX]
H
+ Br
[{RhCpCl2}2] (2.5 mol%)AgSbF6 (10 mol%)Cu(OAc)2 (2.2 eq)
as solvent
PivOH(1.1 eq)
CsOPiv (20 mol%)
160oC, 21h
O
N(i-Pr)2
O
N(i-Pr)2R1
R2
H
R1
Br
R2
yield 16%~89%
R2=H or ortho m/p < 3.0/1
single regiosiomer
O
N(i-Pr)2R1
Br
R2
R1 NH2
R2 R2
[{RhcodCl}2] (2 mol%)Cu(OAc)2 H2O (2.0 eq)
O-xylene, 130oC
R1 NH2
R2 R2
yield 73%~98%H H
5
Alkynylation
Y= DG
2. Oxidative Coupling
HR2 R3+
Rh(III) / [OX] Y
R2/R3
R3/R2
Y
Rh(III)
YY
R2/R3R3/R2
Rh(III)
alkyneinsertion
Alkynylation
NN
Ar
Ar
+
[{RhCpCl2}2] (1.0 mol%)Cu(OAc)2 (1.0 eq)
DMF, 80oC
NN
Ar
Ar
Ar
Ar
yield 20%~99%
T. Satoh, M. Miura, Angew. Chem. Int. Ed. 2008, 47, 4019-4022
NN
Ar
Ar
RhX2-HX
NN
RhX
Ar
Ar
Double C-H Cleavage
NH
R1O
SNH
R1O O
NH
N
OH
NH
R1
O
6
N
O
HH
TsR2-NC+
[{RhCpCl2}2] (2 mol%)Cu(OAc)2 (2.0 eq)
DCE, 130oCN
N R2
O
Ts
yield 40%~81%Z/E = 1:7~ >99:1
RhX
N
O
Ts
CNR2
RhX
N
O
Ts
R2
insertion
Alkynylation
2. Oxidative Coupling
NAcS
O O
R1
R2R
Yield 65%~99%r.r = 1.7/1 ~ 8/1N. Cramer, ACIE, 2012, 51, ASAP
N
R1
R2R
O
R'
Yield 22% ~ 98%T.Rovis, JACS, 2010,132, 10565
O
R5
R6
OR1
R2
R3
R4
Yield 81%~97%T. Satoh, M.MiuraOL, 2007, 9, 1407
NAc
R1
R2
Yield 47% ~ 86%K. Fagnou, JACS, 2008,130, 16474
R
Yield 23%~99%T. Satoh, M.MiuraOL, 2010, 12, 2068
NR
R1 R2
N
R1
R2
Ph
Yield 85%~99%T. Satoh, M.MiuraChem. Commun, 2009, 5141-5143
NAc
NC
R
Ph
Yield 70%~72%
R2O2C
R3 R4
H
NHR1
NAc Ph
R5
R4R3
R2O2C
Yield 31%~81%
F. Glorius, JACS, 2010,132, 9585-9587
C. Zhu, Chem. Eur. J. 2011, 17, 12591-12595
Alkynylation
7
F. Glorius, J. Am. Chem. Soc.,2012,134, 8298-8301
2. Oxidative Coupling
O
H
CN+
[{RhCpCl2}2] (5 mol%)Cu(OAc)2 (2.0 eq)
DMF 100oC
H OR2
R1
R3
R1
R2
CN
R1
R2
Yield 33%~91%
HR3
DG
HR
+ NXS
DG
XR
[{RhCpCl2}2] (1 mol%)AgSbF6 (4 mol%)
PivOH(1.1 eq)
DCE, rt
X=Br, yield 35% ~ 99%X=I, yield 53% ~ 98%
Halogenation(i-Pr)2N O Me2N O n-BuHN O
NH
O
O O
O EtO O NOMe2N
O
Path a : nucleophilic additionPath b : high oxidation-state Rh(V)
Alkynylation
8
B.-Q. Wang, J. Am. Chem. Soc., 2012, 134,16163
Oxidizing DG
DG
HR-H+
Rh(III) / [OX] DGox
HR-H+
Rh(III)DG
R
Oxidizing DG
Yield 27% ~ 95%
N+ EWG
R
OPd(OAc)2 (5 mol%)
NMP, 110 oC
N
R
EWG
HN
R1
R2
R3O
R4+ NsO
HN O
R5
O
Pd(OTs)2(MeCN)2 (10 mol%)
dioxane, 80oC
HN
R1
R2
R3O
R4
NH
R5O O
Yield 45%~90%
Background
X.-L. Cui, Y.-J. Wu, J. Am. Chem. Soc., 2009, 131,13888
2. Oxidative Coupling
W.-Y. Yu, J. Am. Chem. Soc, 2010, 132,12862
R2
N
R3
OAc
R1
Pd(dba)2 (1 mol%)CsCO3 (1.0 eq)
toluene, 150oC
R1
HN
R3
R2
Yield 40%~72%
J. F. Hartwig J. Am. Chem. Soc, 2010, 132, 3676
9
N. Guimond, J. Am. Chem. Soc., 2010, 132, 6908
Oxidizing DG
2. Oxidative Coupling
N. Guimond, J. Am. Chem. Soc, 2011, 133, 6449
NH
O
OMe
R1
R2
R3
+
[{RhCpCl2}2] (1 mol%)CsOAc(30 mol%)
MeOH(0.2 M), 60oC, 16h
NH
O
R1
R2
R3
Yield 48%~90%r.r > 20:1
RhX2
N
R2R3
HOOMe
RhXN
R2R3
OOMe
N
O
R2
R3
ORhX
N
O
R2
R3
XRh
OMe
N-O cleavage
H+NH
O
R2
R3
10
Z.-J. Shi, Angew. Chem. Int. Ed., 2012, 52, 3948
Oxidizing DG
2. Oxidative Coupling
NH
O
O
O
R
NOAc
R1 R2
NH
O
O
R
DG Alkyne/Alkene
HNO
R
N
R1
R2
NH2
O
R
F. Glorius, ACIE, 2012, 51, 7318
F. Glorius, JACS, 2011,133, 2350
S. Chiba, OL, 2010, 12, 5688
Products Reference
O
N
H
O
O R1
R2R
+
[RhCp(MeCN)3(SbF6)2] (5 mol%)
Cu(OAc)2 (20 mol%)
decalin, 120oC
O
R2
R1
R
Yield 12%~90%
C-N Cleavage
RhX2
O
R2R1N
PhPh
carbonylinsertion
Ph
Ph
R2R1N O RhX2
Cu2+ transmetallation
Ph
Ph
R2R1N O CuX
Ph
Ph
O
11
2. Oxidative Coupling
For Rh catalyzed oxidative coupling:
1). Rh(III) is generally efficient catalyst because its high oxidation-state facilitates β-elimination ;
2). Versatile DGs have been well established whereas DG-free coupling reactions are still rare;
3). The fact that more than stoichiometric metal-oxidants (Cu2+, Ag+) are generally needed callsfor eco-friendly pathways (air).
4). Harsh reaction conditions (high temprature, excess oxidant, strong base or acid) lead to poor functional group tolerence.
5). Limited examples involving sp3 C-H activation are reported.
12
DG
H
DG
RhH
[Rh]
Nucleophilic
DG
RhH
X
R2R1
+
DG
XH
R1 R2
Direct Addition
3. Nucleophilic Addition
NBn
H
+ alkyl
Wilkinson's complex
(2 mol%)
toluene, 150oC, 2h
then H+, H2O
O
alkyl
For pioneering work using Ru(0)
R1
O
H
+ R2R1
O
R2
RuH2(CO)(PPh3)3 (4 mol%)
toluene, reflux
Yield 8%~99%
S. Murai, Nature, 366, 529
C.-H. Jun, Angew. Chem. Int. Ed, 2000, 39, 3440
Yield 10%~97%
For Rh(I)
13
3. Nucleophilic Addition
Direct AdditionDirect AdditionDirect Addition
N
R
R2
O
Yield 34%~95%
N
R1
R2
R3
Yield 14%~98% J. A. Ellman,JACS,
2007, 129, 5332
BnN R1
X
R3
R2
Yield 40%~96%ee 70% ~96%
J. A. Ellman,JOC, 2008,73, 6772
N
N
R1
R2
R3
Yield 71%~92%; ee% 71%~97%
J. A. Ellman,Chem. Commun, 2009, 3910
N
X
R1
R2
Yield 55%~96% J. A. Ellman, OL, 2010, 12, 2978
Y
XR1
R2
CO2tBu
n
yield 10%~95%
N
N
N
NO
O
R3
R4
yield 94%~99%, r.r >99:1
S. Chang, Angew. Chem. Int. Ed., 2012, 51, 3677
R
R1
R2
O
N
Yield 27%~96%H.-M. Huang, Chem. Eur. J. 2012, 18, 9511
14
R. G. Bergman, J. A. Ellman, J. Am. Chem. Soc. 2008, 130, 3645
3. Nucleophilic Addition
Direct Addition
[Rh(coe)2Cl]2 (2.5 mol%)
FcPCy2 (10 mol%)NBn R
R'
+toluene, 100oC
NBn
R
R'
NBn
R
R'
[OX] N
R
R'
Yield 32%~88%
NR1
R2
R3
R4
R5
R6
+Rh(1-2.5 mol%)]
then Na(AcO)3BH
NR5
R4
R6
R1
R2
R3
Yield 52%~95%d.r. 10:1~>99:1
R. G. Bergman, J. A. Ellman, J. Am. Chem. Soc. 2012, 134, 4064
15
3. Nucleophilic Addition
Direct Addition
H
H
R1
O
NH
O
.R4
R3
R2
2 mol% [CpRhCl2]2
30 mol% CsOAc
MeOH/H2O = 20/1
-20oC to rt
H
R1
O
NH
O
R4
R2
R3
.
R6
2 mol% [CpRhCl2]2
30 mol% CsOAcMeOH/H2O = 20/1
rt
R7 R5
R1
O
NH
O
R4
R2
R3
R7
R6R5
yield 53% ~ 90%m/d 12/1~30/1
yield 68%~98%
S.-M. Ma, J. Am. Chem. Soc. 2012, 134, 9597
R4R3
R2
R1
H
O
+H2N-R7
R5 R6
[{RhCpCl2}2]AgBF4
Cu(OAc)2
t-amylOH, 110oC
N
R4
R3
R2
R1 R5
R6
R7
BF4-
yield 58%~91%
C.-H. Cheng, Angew. Chem. Int. Ed., 2012, 51, 197
16
3. Nucleophilic Addition
Direct Addition
R. G. Bergman, J. A. Ellman, J. Am. Chem. Soc, 2011. 133, 1248 J. Am. Chem. Soc, 2012. 134, 1482
R. G. Bergman, J. A. Ellman, J. Am. Chem. Soc, 2011. 133, 11430
Others Acceptors
Imine:
Isocyanates:
NH
R2
HR1
O+ R3 NCO
[CpRh(MeCN)3](SbF6)2 (5 mol%)
THF, 16h
NH
R2
R1
O
NHR3
O
Yield 44%~96%
N
R1TsHN
Yield 33%~ 84%
N
R1HO
Yield 17%~ 90%
Aldehyde:
N
H
NPG
R1
+ Rh(III) N
R1
NHPG
Yield 27% ~ 95%
Z.-J. Shi, Org. Lett, 2012, 14, 4498
Z.-J. Shi, Org. Lett, 2012, 14, 636 Org. Lett, 2012, 14, 4498
17
Notes: 1.DG as acceptors; 2. Strained direct addition
3. Nucleophilic Addition
Delayed Addition
DG
H
R1
R2
+
DG
R2/R1R2/R1
Rh H[Rh]
X
R3 R4
Nucleophilicaddition
DG
R2/R1R2/R1
R4
R3XH
insertion
H
NPh
+
R
R
[CpRhCl2]2 (1 mol%)Cu(OAc)2. H2O (1.0 eq)
DMF, 80oC
Ph
R
R Yield 32%~99%
T. Satoh, M. Miura. Chem. Commun. 2009, 5141
NRhX2
RR
Ph
R
R
NPh
RhX2
delayedaddition
beta-hydrogen
elimination
R
R
NPh
H+
?
R
R
NHPh
or Rh(I)
18
N. Cramer, Angew. Chem. Int. Ed, 2010, 49, 8181
N. Cramer, Angew. Chem. Int. Ed, 2011, 50, 11098.
3. Nucleophilic Addition
NH
RAr+ R1 R2
[Rh(cod)OH]2 (1-5mol %) dppp (1.2 eq/Rh)
toluene, 120oC
R NH2
R1
R2
R'yield 55%~98%r.r for 1 = ~2.0/1r.r for 2 > 30/1
1 2
NH
R1
[Rh(cod)OH]2 (5mol %) Ligand (6 mol %)
toluene, 120oC
R1 NH2
R2yield 55%~98%r.r. 2.3\1 ~ >2.0/1
R+
R2
R
P.-J. Zhao, Chem. Eur. J. 2010, 16, 2619
R1
R2NH
R1
[Rh(coe)OH]2 (2.5mol %) Ligand (6 mol %)
toluene, 100-120oC
yield 43%~90%r.r. 2.0\1 ~ >2.0/1ee 76% ~ 96%
R+
R NH2
R2
R1
R
Delayed Addition
19
C.-H. Cheng, Angew. Chem. Int. Ed, 2011, 50, 4169
F. Glorius, J. A m. Chem. Soc. 2011, 133, 2154
3. Nucleophilic Addition
Delayed Addition
R2
R3O
R1yield 61%~93%
R+
R1 OH
R3
R2
R[{RhCpCl2}2] (1 mol%)AgBF4(5 mol%)
Cu(OAc)2H20(2.0 eq)
t-amylOH, 120oC
Ph
R3
Oyield 40%~70%E/Z = 2/1 ~ 3/1
+ R3
R2
R[{RhCpCl2}2] (2.5 mol%)
AgBF4(10 mol%)
Cu(OAc)2 H20(2.1 eq)
dioxane, 140oC
HR1
HR2
R1
Ph
O +
[{RhCpCl2}2] (2.5 mol%)AgBF4(10 mol%)
Cu(OAc)2 H20(2.1 eq)
dioxane, 140oC
R3
HR2
R1 H
Ph
R R3
R1
yield 51%~80%E/Z = 2/1 ~ 3/1
20
3. Nucleophilic Addition
For nucleophilic C-Rh :
1). Rh(I)/Rh(III) are both efficient catalysts ;
2). More type of acceptors are needed to developed and three components reaction has not been reported;
3). Alkenes or other moities that could insert C-Rh bond may take the place of alkynes
4). Limited assymetric examples have been demonstrated, which indicates, in a way, the limitation of existing chiral ligands.
21
4. Other Reactions
M. Murakami, J. A m. Chem. Soc. 2007, 129, 12086
Nucleophilic addition via C-C Cleavage
N
R3
OHR1
R2
+ R
N
R2
R R1 R3
O
+
Yield 33% ~ 94%
[CpRhCl2]2 (2.5 mol%)Ag2CO3 (1.2 eq)
EtOH, 70oC
M. Murakami, J. A m. Chem. Soc.2012, 134, ASAP.
OHR2
R1 +
R3
R4
[Rh(cod)(OH)]2 (2.5 mol%)
toluene, 100oCR1
R2
OH
R3
R4
Yield 69% ~ 96%
OHPh
1
2
2.5 mol% Rh(I) site product
[Rh(cod)(OH)]2
[Rh(cod)(OH)]212 mol % IPr
2
1 Ph
O
80%
Ph
O 89%
PhO
Rh beta-carbonelimination
Rh
Ph
O
Oxidative Coupling via C-C Cleavage
Z.-J. Shi, J. A m. Chem. Soc.2011, 133, 15244.
22
4. Other Reactions
Carboacylation of Olefins
A
X
O
B
R2
R1 [Rh(cod)Cl]2 (2.5/5 mol%)dppb (6/12 mol%)
toluene, 130oC
A
X
BR2 R1
RhO
BA
O
R2R1 R1= H, 61%~94%
R1=R2=H, 35%R2=H, 10%
X
G.-B. Dong, Angew. Chem. Int. Ed, 2012, 51, 7767
Ring Open of VCP
VCP XR
[Rh(CO)2Cl]2 (2.5 mol%)AgSF6 ( 6mol%)
(R)-8H-BINAP (6.5 mol%)
DCE, 50-70 oCX
R
Yield 40%~90%ee 48%~99%
Z.-X. Yu, J. A m. Chem. Soc.2011, 134, 398.
XY
X
Y
R1
R2
HH [Rh(CO)2Cl]2 (5 mol%)
AgSF6 ( 12 mol%) L (25 mol%)
DME, 60-80oCR1
R2
Yield 46%~91%ee 81% ~ 94%
d.r. > 19:1
O
OP N
Et
Et
L
Z.-X. Yu, Angew. Chem. Int. Ed, 2011, 50, 2144 23
5. Conclusion:
25
1). Rh(I)/Rh(III) are versatile catalysts towards C-H bond activation;
2). Necessary DGs limite the substrates scope;
3). Direct sp3 C-H functionalization remains challenging;
4). Mild reaction conditions are demanded for better functional group tolerence.
5). New chiral ligands or novel asymmetric catalytic circles would highlight Rh catalyzed C-H activation.