1 sébastien goudreau literature meeting : 13-02-2007 rhodium(i) chemistry rhodium(i)
TRANSCRIPT
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Sébastien Goudreau
Literature meeting : 13-02-2007
Rhodium(I) ChemistryRhodium(I) Chemistry
Rhodium(I)
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RhodiumRhodium
• Number 45
• [Kr]4d85s1
• Hard silvery white and durable metal that has a high reflectance.(Use in jewellery)
• Does not form an oxide, is not attacked by acids.
• Very high melting point : 2236°C
• It is the most expensive precious metal.
http://en.wikipedia.org/wiki/Rhodium
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ApplicationsApplications
• The primary use of this element is as an alloying agent for hardening platinum and palladium.
• It is used as an electrical contact material due to its low electrical resistance, low and stable contact resistance, and its high corrosion resistance.
• Plated rhodium, made by electroplating or evaporation, is extremely hard and is used for optical instruments.
• This metal finds use in jewelry and for decorations.
• It is also a highly useful catalyst.
http://en.wikipedia.org/wiki/Rhodium
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HistoryHistory
• Rhodium was discovered in 1803 by William Hyde Wollaston soon after his discovery of palladium.
• Wollaston made this discovery in England using crude platinum ore that he presumably obtained from South America.
• His procedure involved dissolving the ore in aqua regia (HCl + HNO3), neutralizing the acid with NaOH.
• He then precipitated the platinum metal by adding NH4Cl, as ammonium chloroplatinate.
• The element palladium was removed as palladium cyanide after treating the solution with mercuric cyanide.
• The material that remained was a red rhodium(III) choride. (Greek rhodon meaning "Rose")
• Wilkinson’s catalyst : RhCl(PPh3)3 : 1965
William Hyde Wollaston
Geoffrey WilkinsonNobel Prize 1973
Wilkinson et al. J. Org. Chen. Chem. Commun., 1965, 7, 131.http://en.wikipedia.org/wiki/Rhodium
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Rhodium(I) in Organic ChemistryRhodium(I) in Organic Chemistry
1) C-H and C-C bond activation
2) HydrorhodationA) HydrogenationB) HydroarylationC) HydroalkynationD) HydroacylationE) HydrosilylationF) Hydroboration
3) AdditionA) 1,4 additionB) 1,2 additionC) Coupling
4) Sigmatropic RearrangementA) CycloadditionB) Alder-ene
5) -Allyl chemistry
6)-aryl elimination
Square plane
RhX
L
L
16e-L
I
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1) C-H and C-C bond activation1) C-H and C-C bond activation
(a) Milstein et al. Angew. Chem. Int. Ed. 2007, 46, ASAP. (b) Bergman et al. J. Am. Chem. Soc. 2006, 128, 2452. (c) Milstein et al. J. Am. Chem. Soc. 2003, 125, 11041.
Prof. David MilsteinThe Weizmann
Institute of Science, Israel
RhLnR' R
Y
LnRhY
R
R'oxydative addition
in C-C bond+
IIII
RhLnLnRh
CH3oxydative addition
in C-C bond+
IIII
H3C
XX
RhLnH R
Y
LnRhY
R
Hoxydative addition
in C-H bond+
IIII
RhLnLnRh
Hoxydative addition
in C-H bond+
IIII
X X
RhLn LnRh
Hoxydative additionin C-H bond
+I IIIH
RR
[1,3]LnRh C
IIIR
vinylydene
RhLnLnRh
R
Hoxydative addition
in C-H bond+
IIIIH Rsp3
sp2
sp
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2) Hydrorhodation2) Hydrorhodation
A) Hydrogenation
B) Hydroarylation
C) Hydroalkynation
D) Hydroacylation
E) Hydrosilylation
F) Hydroboration
RhX
LL
L
Rh
X
L
LZ
H
Rh
X
LL
ZH
Rh
X
LL
Z
Y
RH
YR
H
ZH ZI
III
IIIIII
18e-
18e-
16e-
16e-
R
Y
R
YR
Y
+ H ZY
RH
Z
RhXL3
Z-H activation
oxydative addition
hydrorhodation
migration
reductiveelimination
L
L
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A) HydrogenationA) Hydrogenation
Zassinovich, Mestroni Chem. Rev. 1992, 92, 1051 and references cited therein
Rh ClPh3PPh3P
Rh
Cl
Ph3P
Ph3PH
H
Rh
X
Ph3PPh3P
HH
Rh
X
Ph3PPh3P
H
Y
RH
YR
H
HH HI
III
III
18e-
16e-
16e-
14e-
R
Y
R
YR
Y
+ H HY
RH
H
H-H activation
oxydative addition
hydrorhodation
migration
reductiveelimination
RhCl(PPh3)3
III
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Enantioselective HydrogenationEnantioselective Hydrogenation
CO2Me
N(H)CBz
R CO2Me
N(H)CBz
R
P
P
iPr
iPr
iPr
iPr
[(COD]RhiPrDuPHOS]OTf
iPrDuPHOS
H2 (2 atm), MeOH, rt
CO2Me
N(H)CBzF
CO2Me
N(H)CBz
CO2Me
N(H)CBz
>99% ee 99.4% ee 99.5% ee
Burk et al. J. Am. Chem. Soc. 1993, 115, 10125.
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B) HydroarylationB) Hydroarylation
RhX
LL
L
Rh
X
L
LAr
H
Rh
X
LL
ArH
Rh
X
LL
ArR
H
RH
ArH ArI
III
III
III
18e-
18e-
16e-
16e-
R
R
R
+ H Ar RH
Ar
RhXL3
C-H activationoxydative addition
hydrorhodation
migration
reductiveelimination
L
L
Pfeffer et al. Chem. Rev. 2002, 102, 1731.
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B) Hydroarylation : exempleB) Hydroarylation : exemple
Pfeffer et al. Chem. Rev. 2002, 102, 1731.
12
B) Hydroarylation : exempleB) Hydroarylation : exemple
Pfeffer et al. Chem. Rev. 2002, 102, 1731.
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C) HydroalkynationC) Hydroalkynation
RhX
LL
L
Rh
X
L
L H
Rh
X
LL H
Rh
X
LL
RH
RH
HI
III
III
III
18e-
18e-
16e-
16e-
R
R
R
+ H RHRhXL3
C-H activationoxydative addition
hydrorhodation
migration
reductiveelimination
L
L
Pfeffer et al. Chem. Rev. 2002, 102, 1731.
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C) Hydroalkynation : exemplesC) Hydroalkynation : exemples
Pfeffer et al. Chem. Rev. 2002, 102, 1731.
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D) HydroacylationD) Hydroacylation
RhX
LL
L
Rh
X
L
L H
Rh
X
LL H
Rh
X
LL
RH
R
H
HI
III
III
III
18e-
18e-
16e-
16e-
R
R
R
+RhXL3
C-H activationoxydative addition
hydrorhodation
migration
reductiveelimination
L
L
R'
Y
YR'
YR'
YR'
Y
R'
R
HY
R'H R'
Y
Pfeffer et al. Chem. Rev. 2002, 102, 1731.
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D) Hydroacylation : exemplesD) Hydroacylation : exemples
Pfeffer et al. Chem. Rev. 2002, 102, 1731.
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D) Hydroacylation : exampleD) Hydroacylation : example
Pfeffer et al. Chem. Rev. 2002, 102, 1731.
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Intramolecular HydroacylationIntramolecular Hydroacylation
Pfeffer et al. Chem. Rev. 2002, 102, 1731.
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C) HydrosilylationC) Hydrosilylation
RhX
LL
L
Rh
X
L
LSiR'3
H
Rh
X
LL
SiR'3H
Rh
X
LL
SiR'3
Y
RH
YR
H
R'3SiH SiR'3I
III
IIIIII
18e-
18e-
16e-
16e-
R
Y
R
YR
Y
+ H SiR'3Y
RH
R'3Si
RhXL3
Si-H activation
oxydative addition
hydrorhodation
migration
reductiveelimination
L
L
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C) HydrosilylationC) Hydrosilylation
R1 R2
O
Si HR'R
R'' R1 R2
OSi
R
R''R'
R1 R2
OHH3O+cat
+
R1 R2
N
Si HR'R
R'' R1 R2
NSi
R
R''R'
R1 R2
NHH3O+cat
+
R3
R3R3
R1 R2
Si HR'R
R''
OSi
R
R''R'
H3O+cat+
O
X
X
R1 R2
H
O
X
R1 R2
H
Eor E+
R1 R2 Si HR'R
R'' R1 R2
Si
R
R''R'
cat+
R1Si HR'
R
R'' R1
Si
R
R''R'
cat+
Pfeffer et al. Chem. Rev. 2002, 102, 1731.
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D) HydroborationD) Hydroboration
Guiry et al. Adv. Synth. Catal. 2005, 347, 609.
RhX
LL
L
Rh
X
L
LB
H
Rh
X
LL H
Rh
X
LL
BR
H
H BI
III
III
III
18e-
18e-
16e-
16e-
R
R
R
+ RH
B
RhXL3
Si-H activation
oxydative addition
hydrorhodation
migration
reductiveelimination
L
L
O
O
OO
BOO
OO
H BO
OO
OR
B
H
OO
+
Rh
X
LL
BH
III
16e-
OO
R
or
RH
BO
ORB
H
OO +
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D) HydroborationD) Hydroboration
Guiry et al. Adv. Synth. Catal. 2005, 347, 609.
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Hydrorhodation : ConclusionHydrorhodation : Conclusion
• Atom efficient
• Mild conditions
• Good alternative route
• Regioselectivity : can be problematic
• Enantioselectivity : can be very good
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2) Addition reaction2) Addition reaction
A) 1,4 addition
B) 1,2 addition
C) Coupling
Y
X
R M
RhLn
Y
X
R' R
R'
R' Y
X
R M
RhLn
RY
X
R'
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A) 1,4 addition reactionA) 1,4 addition reaction
M : Organoboron (organostannate, organosilane, organobismuth)R : Aryl
Fagnou, Lautens Chem. Rev. 2003, 103, 169.
Y
X
R M
RhLn
Y
X
R' R
R'
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A) 1,4 Addition : exemplesA) 1,4 Addition : exemples
Fagnou, Lautens Chem. Rev. 2003, 103, 169.
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A) 1,4 Addition : examplesA) 1,4 Addition : examples
Fagnou, Lautens Chem. Rev. 2003, 103, 169.
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A) 1,4 Addition : examplesA) 1,4 Addition : examples
Fagnou, Lautens Chem. Rev. 2003, 103, 169.
29
A) 1,4 Addition : examplesA) 1,4 Addition : examples
Fagnou, Lautens Chem. Rev. 2003, 103, 169.
30
Fagnou, Lautens Chem. Rev. 2003, 103, 169.
A) 1,4 Addition : examplesA) 1,4 Addition : examples
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Krische’s chemistryKrische’s chemistry
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Krische’s chemistryKrische’s chemistry
Krische et al. J. Am. Chem. Soc. 2002, 124, 15156.
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B) 1,2 Addition reactionB) 1,2 Addition reaction
Fagnou, Lautens Chem. Rev. 2003, 103, 169.
M : Organoboron (organostannate, organosilane, organobismuth)R : Aryl
R' Y
X
R M
RhLn
RY
X
R'
34
B) 1,2 Addition : exemplesB) 1,2 Addition : exemples
Fagnou, Lautens Chem. Rev. 2003, 103, 169.
35
Ellman et al. J. Am. Chem. Soc. 2005, 127, 1092.
B) 1,2 Addition : exemplesB) 1,2 Addition : exemples
36
(a) Fagnou, Lautens Chem. Rev. 2003, 103, 169. (b) Iwasawa et al. J. Am. Chem. Soc. 2006, 128, 8706.
B) 1,2 Addition : exemplesB) 1,2 Addition : exemples
37
Krische’s chemistryKrische’s chemistry
Krische et al. J. Am. Chem. Soc. 2006, 128, 718.
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C) CouplingC) Coupling
Fagnou, Lautens Chem. Rev. 2003, 103, 169.
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Addition reaction : ConclusionAddition reaction : Conclusion
• Mild conditions : presence of water
• Good enantioselectivity
• Excess of organoboron needed
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4) Sigmatropic rearrangement4) Sigmatropic rearrangement
A) Cycloaddition
B) Alder-ene
2+2+22+2+1 (Pauson-Khand)3+24+25+26+14+2+2
Paul A. WenderStanford University, USA
H HAlder-ene
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Mecanism : [2+2+2]Mecanism : [2+2+2]
R3
R4
R1
R2
oxydativecoupling
RhLn RhLn
I IIIR1
R2
R4R3
RhLn
IIIR1
R2
R4R3
R5
R6 RhLn
R6R5
R2
R1
R3 R4
insertion
R2
R5
R6
R4R3
R1
reductiveelimination
III
RhLn+I
RhLn
R6R5
R2
R1
R3 R4
III
R7
R8
reductiveelimination
R1
R3 R4
R2
RhLn+I
R3
R4
R1
R2R7
R8
RhLn
IR2
R5
R6
R4R3
R1
Lautens et al. Chem. Rev. 1996, 96, 49.
42
[2+2+1] Cycloaddition : Pauson-Khand Reaction[2+2+1] Cycloaddition : Pauson-Khand Reaction
R oxydativecoupling
RhLn RhLnI III
RhLn
III
R
C insertion
reductiveelimination
III
RhLn
+I
reductiveelimination
RhLn+I
RhLn
I
X X
H
R
R
X
RhLn
X
R
H
-hydride
reductiveelimination
X
R
RhLn+I
OCO
X
H
RhLnX
H
R
O
IIIRhLnX
H
R
O
R
X
H
O
or
R
X
R
X
H
O
X
CO+
Lautens et al. Chem. Rev. 1996, 96, 49.
43
[2+2+1] Cycloaddition : Pauson-Khand Reaction[2+2+1] Cycloaddition : Pauson-Khand Reaction
Jeong et al. J. Am. Chem. Soc. 2000, 122, 6771.
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[3+2] Cycloaddition[3+2] Cycloaddition
RhLn
I
Ph R
O
Ph Ph
O
Ph Ph
RPh
Ph
R
oxydativecoupling
RhLn RhLn
I III
RPh
Ph
R
reductiveelimination
Ph
Ph R
Ph
RhLn+I
O
PhPh
OPh
Ph
O
RhLn
III
RPh
OPh
Ph
O
Ph Ph
RPh
[2,2]
Wender et al. J. am. Chem. Soc. 2006, 128, 14814.
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[4+2] Cycloaddition : Diels Alder[4+2] Cycloaddition : Diels Alder
Mikami et al. J. Am. Chem. Soc. 2006, 128, 12648.
oxydativecoupling
RhLn RhLn
I III
reductiveelimination
RhLn +I
RhLn
I
X
R1
X
R1
X
R2
R1
RhLn
RhLn
III
X
R1
R2
X
R1
R2
III
R2
X
R2
X
R1
R2
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[5+2] Cycloaddition[5+2] Cycloaddition
Saito et al. J. Org. Chem. 2006, 71, 6437.
47
[6+1] cycloaddition[6+1] cycloaddition
Wender et al. Angew. Chem. Int. Ed. 2006, 45, 3957.
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[4+2+2] and [2+2+2+1] cycloaddition[4+2+2] and [2+2+2+1] cycloaddition
Ojima et al. Org. Lett. 2004, 6, 3589.Wender et al. J. Am. Chem. Soc. 2006, 128, 5354.
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B) Alder-eneB) Alder-ene
Zhang et al. J. Am. Chem. Soc. 2002, 124, 8198.
Ph oxydativecoupling
RhLn RhLnI III
reductiveelimination
RhLn+I
RhLn
I
O O
Ph-hydride
O
H
O
RhLn
IIIO
PhO
H O
O
Ph
O O OO
Ph
PhH H
Alder-ene
H
H
50
ConclusionConclusion
• Access to a large variety of cycles
• Regioselectivity : need linkers
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5) Allylic5) Allylic
R
O
O
MeO
Rh
R- MeOCOO-
Nu
RhLnI
IIIR
NuRhLnI
-
(a) P.A. Evans et al. J. Am. Chem. Soc. 2004, 126, 8642. (b) P.A. Evans et al. J. Am. Chem. Soc. 2003, 125, 8974. (c) P.A. Evans et al. J. Am. Chem. Soc. 2002, 124, 7882.
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6) 6) -aryl elimination-aryl elimination
John F. HartwigYale University, USA
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ConclusionConclusion
1) C-H and C-C bond activation
2) HydrorhodationA) HydrogenationB) HydroarylationC) HydroalkynationD) HydroacylationE) HydrosilylationF) Hydroboration
3) AdditionA) 1,4 additionB) 1,2 additionC) Coupling
4) Sigmatropic RearrangementA) CycloadditionB) Alder-ene
5) -Allyl chemistry
6)-aryl elimination
Square plane
RhX
L
L
16e-L
I
54
ConclusionConclusion