carbon monoxide “insertion” siyu ye 2008.1.25. 22 the term “insertion” is used to describe...
TRANSCRIPT
![Page 1: Carbon Monoxide “Insertion” Siyu Ye 2008.1.25. 22 The term “insertion” is used to describe the process whereby an unsaturated moiety, which may or may](https://reader035.vdocument.in/reader035/viewer/2022062518/56649f255503460f94c3c08c/html5/thumbnails/1.jpg)
Carbon Monoxide “Insertion”
Siyu Ye
2008.1.25
![Page 2: Carbon Monoxide “Insertion” Siyu Ye 2008.1.25. 22 The term “insertion” is used to describe the process whereby an unsaturated moiety, which may or may](https://reader035.vdocument.in/reader035/viewer/2022062518/56649f255503460f94c3c08c/html5/thumbnails/2.jpg)
22
The term “insertion” is used to describe the process whereby an
unsaturated moiety, which may or may not be coordinated to the
metal initially, becomes bonded to the metal and to a saturated ligand
(which was initially attached to the metal center).
M X
M A B XA B
C
M C X
Anderson, G. K.; Cross, R. J. Acc. Chem. Res. 1984,17, 67.
Y M XY M C X
O
Y C X
OCO
![Page 3: Carbon Monoxide “Insertion” Siyu Ye 2008.1.25. 22 The term “insertion” is used to describe the process whereby an unsaturated moiety, which may or may](https://reader035.vdocument.in/reader035/viewer/2022062518/56649f255503460f94c3c08c/html5/thumbnails/3.jpg)
33
Content
1. Introduction
2. Acid Induced Carbonylation
3. Main Group Metal Induced Carbonylation
4. Transition Metal Induced Carbonylation
5. Conclusion
Background
Methanol Carbonylation
Hydroformylation
Double Carbonylation
![Page 4: Carbon Monoxide “Insertion” Siyu Ye 2008.1.25. 22 The term “insertion” is used to describe the process whereby an unsaturated moiety, which may or may](https://reader035.vdocument.in/reader035/viewer/2022062518/56649f255503460f94c3c08c/html5/thumbnails/4.jpg)
44
Content
1. Introduction
2. Acid Induced Carbonylation
3. Main Group Metal Induced Carbonylation
4. Transition Metal Induced Carbonylation
5. Conclusion
Background
Methanol Carbonylation
Hydroformylation
Double Carbonylation
![Page 5: Carbon Monoxide “Insertion” Siyu Ye 2008.1.25. 22 The term “insertion” is used to describe the process whereby an unsaturated moiety, which may or may](https://reader035.vdocument.in/reader035/viewer/2022062518/56649f255503460f94c3c08c/html5/thumbnails/5.jpg)
5
The CO Molecule
C+O-, electronegativity
C-O+, a low dipole moment of 0.112 D
Molecular Orbital of Carbon Monoxide
C O
C O
C O
C O
C O
n
*
*
Henrici-Olivé, G.; Olivé, S. The Chemistry of the Catalyzed Hydrogenation of Carbon Monoxide; Springer-Verlag: Berlin, Heidelberg, New York, Tokyo, 1984; p 23.
5
LUMO
HOMO
![Page 6: Carbon Monoxide “Insertion” Siyu Ye 2008.1.25. 22 The term “insertion” is used to describe the process whereby an unsaturated moiety, which may or may](https://reader035.vdocument.in/reader035/viewer/2022062518/56649f255503460f94c3c08c/html5/thumbnails/6.jpg)
6
M X
M X
CO
M X
CO
M C X
O
M C X
OX migration
CO migration
CO
Migratory Insertion
Which is more appropriate?
![Page 7: Carbon Monoxide “Insertion” Siyu Ye 2008.1.25. 22 The term “insertion” is used to describe the process whereby an unsaturated moiety, which may or may](https://reader035.vdocument.in/reader035/viewer/2022062518/56649f255503460f94c3c08c/html5/thumbnails/7.jpg)
77
Calderazzo, F. Angew. Chem., Int. Ed. 1977, 16, 299.
Brunner, H.; Vogt, H. Angew. Chem., Int. Ed. 1981, 20, 405.
FeOCMe
LFeOC L
O
Fe LO
CO
Mn
CO
O
13COOC
OC COMn
CO
COMeOC
OC COMn
CO
CO13COOC
Me COMn
CO
CO13COOC
OC Me+ +
A B C
(A:B:C = 1:1:2)
Mn
CO
COMeOC
OC CO13CO Mn
CO
O
13COOC
OC CO+alkyl migration
CO migration
![Page 8: Carbon Monoxide “Insertion” Siyu Ye 2008.1.25. 22 The term “insertion” is used to describe the process whereby an unsaturated moiety, which may or may](https://reader035.vdocument.in/reader035/viewer/2022062518/56649f255503460f94c3c08c/html5/thumbnails/8.jpg)
88
Influence Factors
Cavell, K. J. Coord. Chem. Rev. 1996, 155, 209.
cis-(CO/Me)
trans-(P/Me), ligand with a large trans influence
θ, angle of L-M-X
partial negative charge at alkyl group
partial positive charge at CO
Pt
Me
CO
PH3
F
Pt
Me
CO
PH3
F
Pt C
PH3
FMe
O
![Page 9: Carbon Monoxide “Insertion” Siyu Ye 2008.1.25. 22 The term “insertion” is used to describe the process whereby an unsaturated moiety, which may or may](https://reader035.vdocument.in/reader035/viewer/2022062518/56649f255503460f94c3c08c/html5/thumbnails/9.jpg)
9
Absence of Acyl-to-CO Migration
Ni-C (acetyl) bond (184 pm) < Ni-C σ bond (194 pm)
Ti-C (acetyl) bond (207 pm) < Ti-C σ bond (214 pm)
M-C (acetyl) bond, a partial double bond
9
Henrici-Olivé, G.; Olivé, S. The Chemistry of the Catalyzed Hydrogenation of Carbon Monoxide; Springer-Verlag: Berlin, Heidelberg, New York, Tokyo, 1984; p 79.
Ni
P(CH3)3
Cl
P(CH3)3O
Ti Cl
O
Mn(CO)5O Mn(CO)5
O
O258 atm CO
80 oC
O
Cl
O
NaMn(CO)5 Mn(CO)5O
O
Mn(CO)5O
CH3Mn(CO)5+ +decomposed
![Page 10: Carbon Monoxide “Insertion” Siyu Ye 2008.1.25. 22 The term “insertion” is used to describe the process whereby an unsaturated moiety, which may or may](https://reader035.vdocument.in/reader035/viewer/2022062518/56649f255503460f94c3c08c/html5/thumbnails/10.jpg)
1010
Content
1. Introduction
2. Acid Induced Carbonylation
3. Main Group Metal Induced Carbonylation
4. Transition Metal Induced Carbonylation
5. Conclusion
Background
Methanol Carbonylation
Hydroformylation
Double Carbonylation
![Page 11: Carbon Monoxide “Insertion” Siyu Ye 2008.1.25. 22 The term “insertion” is used to describe the process whereby an unsaturated moiety, which may or may](https://reader035.vdocument.in/reader035/viewer/2022062518/56649f255503460f94c3c08c/html5/thumbnails/11.jpg)
1111
R OH COOHRCO, H2O
H+
R OH R OH2+ R
R R CO+ COOHR
H+
H2O -H+CO
OCO
HF-TaF5
+OC
OH O
H+ CO
-H+
Koch carbonylation
Farcasiu, D.; Schlosberg, R. H. J. Org. Chem. 1982, 47, 151.
Acid Induced Carbonylation
![Page 12: Carbon Monoxide “Insertion” Siyu Ye 2008.1.25. 22 The term “insertion” is used to describe the process whereby an unsaturated moiety, which may or may](https://reader035.vdocument.in/reader035/viewer/2022062518/56649f255503460f94c3c08c/html5/thumbnails/12.jpg)
1212
Content
1. Introduction
2. Acid Induced Carbonylation
3. Main Group Metal Induced Carbonylation
4. Transition Metal Induced Carbonylation
5. Conclusion
Background
Methanol Carbonylation
Hydroformylation
Double Carbonylation
![Page 13: Carbon Monoxide “Insertion” Siyu Ye 2008.1.25. 22 The term “insertion” is used to describe the process whereby an unsaturated moiety, which may or may](https://reader035.vdocument.in/reader035/viewer/2022062518/56649f255503460f94c3c08c/html5/thumbnails/13.jpg)
1313
Li Induced Carbonylation
n-BuLi + CO n-BuC(O)Li n-BuC(O)SiMe3-110 oC Me3SiCl
77 %
Seyferth, D.; Weinstein, R. M. J. Am. Chem. Soc. 1982, 104, 5534.
Song, Q.; Chen, J.; Jin, X.; Xi, Z. J. Am. Chem. Soc. 2001, 123, 10419.
I
IO
Ph
Ph
73 %
1) 4 eq t-BuLi, -78 oC, 1h2) CO, -78 oC, 1h
3) 2 eq PhCH2Br, -78 oC to r.t., 1h
![Page 14: Carbon Monoxide “Insertion” Siyu Ye 2008.1.25. 22 The term “insertion” is used to describe the process whereby an unsaturated moiety, which may or may](https://reader035.vdocument.in/reader035/viewer/2022062518/56649f255503460f94c3c08c/html5/thumbnails/14.jpg)
1414
Mg Induced Carbonylation
EtMgBr
Et MgBr
O
Et Et
OEt
OMgBr
Et
MgBr
Et2CHOHEt
O O
MgBr
Et
O O
Et Et
O OH
Et
Et
O OMgBrMgBr
Et
COHMPT
EtMgBr
EtMgBr
H2O
H2O
EtBr
EtBr
CO
Sprangers, W. J. J. M.; Louw, R. J. Chem. Soc., Perkin Trans. 2 1976, 1895.
HMPT = PNN
N
![Page 15: Carbon Monoxide “Insertion” Siyu Ye 2008.1.25. 22 The term “insertion” is used to describe the process whereby an unsaturated moiety, which may or may](https://reader035.vdocument.in/reader035/viewer/2022062518/56649f255503460f94c3c08c/html5/thumbnails/15.jpg)
15
Al Induced Carbonylation
15
2 t-Bu3Al 2 CO Alt-Bu
Ot-Bu
t-Bu
Alt-Bu
Ot-Bu
t-Bu
+20 oC
hexanes
Mason, M. R.; Song, B.; Kirschbaum, K. J. Am. Chem. Soc. 2004, 126, 11812.
![Page 16: Carbon Monoxide “Insertion” Siyu Ye 2008.1.25. 22 The term “insertion” is used to describe the process whereby an unsaturated moiety, which may or may](https://reader035.vdocument.in/reader035/viewer/2022062518/56649f255503460f94c3c08c/html5/thumbnails/16.jpg)
1616
Content
1. Introduction
2. Acid Induced Carbonylation
3. Main Group Metal Induced Carbonylation
4. Transition Metal Induced Carbonylation
5. Conclusion
Background
Methanol Carbonylation
Hydroformylation
Double Carbonylation
![Page 17: Carbon Monoxide “Insertion” Siyu Ye 2008.1.25. 22 The term “insertion” is used to describe the process whereby an unsaturated moiety, which may or may](https://reader035.vdocument.in/reader035/viewer/2022062518/56649f255503460f94c3c08c/html5/thumbnails/17.jpg)
17
Transition Metal Induced Carbonylation
17
Chiusoli, G. P. Acc. Chem. Res. 1973, 6, 422.
X COO
O+
Ni(CO)4 or Pd(0)
MeOH
M
O
M
R
O
X
M X
M X
CO
X
X
CO
![Page 18: Carbon Monoxide “Insertion” Siyu Ye 2008.1.25. 22 The term “insertion” is used to describe the process whereby an unsaturated moiety, which may or may](https://reader035.vdocument.in/reader035/viewer/2022062518/56649f255503460f94c3c08c/html5/thumbnails/18.jpg)
1818
Heck, R. F. J. Am. Chem. Soc. 1963, 85, 2013.
HH + CO + H2OOH
O
Ni2+,Cu2+
8~12 MPa, 150~250oC
Reppe process
Schoenberg, A.; Bartoletti, I.; Heck, R. F. J. Org. Chem. 1974, 39, 23.
R CO HXR
O
OR'+ +
Ni(CO)4
R'OH
BrO
O
Bu
PdBr2(PPh3)2, CO,n-BuOH, n-Bu3N
100 oC, 1 atm
![Page 19: Carbon Monoxide “Insertion” Siyu Ye 2008.1.25. 22 The term “insertion” is used to describe the process whereby an unsaturated moiety, which may or may](https://reader035.vdocument.in/reader035/viewer/2022062518/56649f255503460f94c3c08c/html5/thumbnails/19.jpg)
19
CO-to-C—X Insertion
1919
Heck, R. F. J. Am. Chem. Soc. 1963, 85, 1460.
HCo(CO)4 CO (CH2)2COCo(CO)4R
R
OH
O O
O+ +
N(Cy)2Et+ (Cy)2N+HEt Co(CO)4
-
Wang, M. D.; Alper, H. J. Am. Chem. Soc. 1992, 114, 7018.
N R
R'
N
N
R'
O R
R'
O
R
R' = Me, Ph, CH2Ph, CH2OCH3, CH2COOEt
(30~61%)
(15~56 %)
Co2(CO)8
CO, 54 atm, 220 oC
R = alkyl
R = aryl
![Page 20: Carbon Monoxide “Insertion” Siyu Ye 2008.1.25. 22 The term “insertion” is used to describe the process whereby an unsaturated moiety, which may or may](https://reader035.vdocument.in/reader035/viewer/2022062518/56649f255503460f94c3c08c/html5/thumbnails/20.jpg)
2020
Pauson-Khand Reaction
NTs N OTs
10 mol% PdCl210 mol% tmtu
1 atm CO, THF50 oC, 36 h, 92%
N N
S
tmtu =
Tang, Y.; Deng, L.; Zhang, Y.; Dong, G.; Chen, J.; Yang, Z. Org. Lett. 2005, 7, 1657.
OTBDPS
Co2(CO)6
O
H HH
OTBDPS
triquinane
6 eq. TMANO (anhydrous)
CH2Cl2, -78 oC to r.t. 85%
TMANO = N O
Paquette, L. A.; Borrelly, S. J. Org. Chem. 1995, 60, 6912.
Co2(CO)6
+
O
![Page 21: Carbon Monoxide “Insertion” Siyu Ye 2008.1.25. 22 The term “insertion” is used to describe the process whereby an unsaturated moiety, which may or may](https://reader035.vdocument.in/reader035/viewer/2022062518/56649f255503460f94c3c08c/html5/thumbnails/21.jpg)
2121
Complicated Carbonylation
Negishi, E.-I.; Coperet, C.; Ma, S.; Mita, T.; Sugihara, T.; Tour, J. M. J. Am. Chem. Soc. 1996, 118, 5904.
Aksin, O.; Dege, N.; Artok, L.; Turkmen, H.; Cetinkaya, B. Chem. Commun. 2006, 3187.
R
R
B(OH)2
R'
O
R'
RR
O
[Rh(cod)Cl]2 20 atm CO
toluene80 oC,16 h
+
I
OSiR3 OSiR3
O
75 %, trans/cis = 3:1
PdCl2(PPh3)2, MeOH
15 bar CO, 100 oC
OMeO
![Page 22: Carbon Monoxide “Insertion” Siyu Ye 2008.1.25. 22 The term “insertion” is used to describe the process whereby an unsaturated moiety, which may or may](https://reader035.vdocument.in/reader035/viewer/2022062518/56649f255503460f94c3c08c/html5/thumbnails/22.jpg)
2222
Me
BnO
O
MeMe
BnOCO+
5 mol% [Rh(cod)Cl]2 10 mol% DPPP
p-xylene130 oC, 2.5 h
(1 atm)
84 %
Matsuda, T.; Tsuboi, T.; Murakami, M. J. Am. Chem. Soc. 2007, 129, 12596.
Kramer, J. W.; Joh, D. Y.; Coates, G. W. Org. Lett. 2007, 9, 5581.
OR'
R
OHO
RR' O
OH
CO2 mol% HCo(CO)4
1.0 M DME60 oC, 24 h
+
(800 psi)
![Page 23: Carbon Monoxide “Insertion” Siyu Ye 2008.1.25. 22 The term “insertion” is used to describe the process whereby an unsaturated moiety, which may or may](https://reader035.vdocument.in/reader035/viewer/2022062518/56649f255503460f94c3c08c/html5/thumbnails/23.jpg)
23
Wang, Y.; Wang, J.; Su, J.; Huang, F.; Jiao, L.; Liang, Y.; Yang, D.; Zhang, S.; Wender, P. A.; Yu, Z.-X. J. Am. Chem. Soc. 2007, 129, 10060.
X
O
X
[Rh(CO)2Cl]2, COdioxane, 80 oC
ArICO2EtH
N2
CO2Et
N2
Ar
O
+
10% Pd(PPh3)4, Et3N, Bu4NBr,
CO balloon,MeCN, 45 oC
Peng, C.; Cheng, J.; Wang, J. J. Am. Chem. Soc. 2007, 129, 8708.
![Page 24: Carbon Monoxide “Insertion” Siyu Ye 2008.1.25. 22 The term “insertion” is used to describe the process whereby an unsaturated moiety, which may or may](https://reader035.vdocument.in/reader035/viewer/2022062518/56649f255503460f94c3c08c/html5/thumbnails/24.jpg)
2424
Content
1. Introduction
2. Acid Induced Carbonylation
3. Main Group Metal Induced Carbonylation
4. Transition Metal Induced Carbonylation
5. Conclusion
Background
Methanol Carbonylation
Hydroformylation
Double Carbonylation
![Page 25: Carbon Monoxide “Insertion” Siyu Ye 2008.1.25. 22 The term “insertion” is used to describe the process whereby an unsaturated moiety, which may or may](https://reader035.vdocument.in/reader035/viewer/2022062518/56649f255503460f94c3c08c/html5/thumbnails/25.jpg)
2525
Methanol Carbonylation
Forster, D. J. Am. Chem. Soc. 1976, 98, 846.
CH3OH + CO CH3COOH
CH3COOH CH3OH+ CH3COOCH3 + H2O
CH3COOCH3 + CO (CH3CO)2O
RhI
I CO
CO
RhI
I CO
CO
CH3
I
RhI
I CO
COI
H3C
RhI
I CO
CO
CO
I
CH3CO
CH3COI
CH3I
H2O/CH3OH
CH3COOH/CH3COOCH3
slow
Monsanto process
![Page 26: Carbon Monoxide “Insertion” Siyu Ye 2008.1.25. 22 The term “insertion” is used to describe the process whereby an unsaturated moiety, which may or may](https://reader035.vdocument.in/reader035/viewer/2022062518/56649f255503460f94c3c08c/html5/thumbnails/26.jpg)
2626
RhI
I CO
CO
RhI
I CO
CO
CH3
I
RhI
I CO
COI
H3C
RhI
I CO
CO
CO
I
CH3CO
CH3COI
CH3I slow
CH3COOCH3
(CH3CO)2O
slow
殷元骐 主编 , 《羰基合成化学》 , p 167.
RhI
I CO
CO
RhI
I CO
CO
CH3
I
RhI
I CO
COI
H3C
RhI
I CO
CO
CO
I
CH3CO
CH3COI
CH3I slowCH3COOCH3
(CH3CO)2O
CH3COOLiLiI
![Page 27: Carbon Monoxide “Insertion” Siyu Ye 2008.1.25. 22 The term “insertion” is used to describe the process whereby an unsaturated moiety, which may or may](https://reader035.vdocument.in/reader035/viewer/2022062518/56649f255503460f94c3c08c/html5/thumbnails/27.jpg)
27
Hydroformylation
27殷元骐 主编 , 《羰基合成化学》 , p 4.
RR
OR
O
CO H2cat
+ + +
n iso
HCo(CO)4 HCo(CO)3
-CO
+CO
HCo(CO)3
O
(OC)3Co
CO
H2
H
O
(OC)3Co
(OC)4Co
(OC)3Co
(OC)4Co
O
(OC)3Co
O
H
H2
CO
iso
n
typical condition: 110~180 , 20~35 MPa℃double bond isomerization, 110 , p(CO) = ℃ 9.0 MPa, 1-pentene vs. 2-pentene, the same
n/iso ratio100 , p(CO) from 0.25 MPa to 9.0 MPa, ℃ n/iso from 1.6 to 4.4high p(CO), high p(H2)
![Page 28: Carbon Monoxide “Insertion” Siyu Ye 2008.1.25. 22 The term “insertion” is used to describe the process whereby an unsaturated moiety, which may or may](https://reader035.vdocument.in/reader035/viewer/2022062518/56649f255503460f94c3c08c/html5/thumbnails/28.jpg)
2828
Jackson, W. R.; Perlmutter, P.; Suh, G.-H. J. Chem. Soc., Chem. Commun. 1987, 40, 129.Couthino, K. J. et. al. J. Chem. Soc., Dalton Trans. 1997, 3193.
PPh2
PPh2
OHRh2(OAc)4/PPh3 CO/H2
86%
O
O
O
O+
Rh-TPPTS CO/H2
HO OH
Nair, V. S. et. al. Rec. Adv. Basic Appl. Aspects Industr. Catal. 1998, 113, 529.
TPPTS = P(m-C6H4SO3Na)3
OH
O OMeCO/H2(1:1), MeOH Rh6(CO)16/PPh3
63-84 bar, 150 oC
Smith, W. E. et. al. In Catalysis of Organic Reactions; Augustine, R. L., Ed.; Dekker: New York, 1985; p 151.
![Page 29: Carbon Monoxide “Insertion” Siyu Ye 2008.1.25. 22 The term “insertion” is used to describe the process whereby an unsaturated moiety, which may or may](https://reader035.vdocument.in/reader035/viewer/2022062518/56649f255503460f94c3c08c/html5/thumbnails/29.jpg)
2929
NR2
HNR2+
CO/H2(1:1) [Rh(cod)Cl]280 bar, 20 h, 80 oC
81-93%
HNR2 = diethylamine, morpholine
Kranemann, C. L.; Eilbracht, P. Synthesis 1998, 71.
R3R2
R1
R3R2
R1
O
R3R2
R1
OH
R3R2
R1
O
OH
R3R2
R1
O
CO/H2(1:1) RhCl(PPh3)3
100 bar, 70 h, 130 oC
a: R1 = CH3, R2 = R3 = H, 21% b: R1 = H, R2 = R3 = CH3, 40%
Roggenbuck, R.; Eilbracht, P. Tetrahedron Lett. 1999, 40, 7455.
![Page 30: Carbon Monoxide “Insertion” Siyu Ye 2008.1.25. 22 The term “insertion” is used to describe the process whereby an unsaturated moiety, which may or may](https://reader035.vdocument.in/reader035/viewer/2022062518/56649f255503460f94c3c08c/html5/thumbnails/30.jpg)
3030
Asymmetric Hydroformylation
Breit, B. Acc. Chem. Res. 2003, 36, 264.
Sakai, N.; Mano, S.; Nozaki, K.; Takaya, H. J. Am. Chem. Soc. 1993, 115, 7033.
Difficulties : 1. High regioselectivity
2. High enantioselectivity
3. No racemization of aldehyde
RR
OR
O
+
Rh(I)/L*CO/H2
linear branched
R = Ph 12 : 88 (94% ee)R = Et 79 : 21 (83% ee)R = OAc 14 : 86 (92% ee)R = 13 : 87 (96% ee)
L* = (R,S)-BINAPHOS
PPh2O
PO
O
![Page 31: Carbon Monoxide “Insertion” Siyu Ye 2008.1.25. 22 The term “insertion” is used to describe the process whereby an unsaturated moiety, which may or may](https://reader035.vdocument.in/reader035/viewer/2022062518/56649f255503460f94c3c08c/html5/thumbnails/31.jpg)
3131
Diastereoselective Hydroformylation
Breit, B.; Zahn, S. K. Angew. Chem., Int. Ed. 1999, 38, 969.
O O
PPh2
R
R
O(o-DPPB)
O
R
O(o-DPPB)
O
+
Rh-cat.CO/H2
55-99%
syn anti
96 : 4up to
Breit, B. Angew. Chem., Int. Ed. 1996, 35, 2835.
R
O(o-DPPB)
R
O(o-DPPB)
O
R'
36-70%
R
O(o-DPPB)
O
R'R
O(o-DPPB)
OWittig olefination
hydroformylation hydrogenation
0.7 mol% RhH(CO)(PPh3)3, 1.1 eq Ph3P=CHCOR', 20 bar CO/H2(1:1), toluene, 90 oC, 48 h
syn:anti 90:10
![Page 32: Carbon Monoxide “Insertion” Siyu Ye 2008.1.25. 22 The term “insertion” is used to describe the process whereby an unsaturated moiety, which may or may](https://reader035.vdocument.in/reader035/viewer/2022062518/56649f255503460f94c3c08c/html5/thumbnails/32.jpg)
32
Double Carbonylation
32
R X + 2CO + NuH R
O
O
Nu + HXCo or Pd cat.
NuH = R'NH2, R'OH, H2O
殷元骐 主编 , 《羰基合成化学》
(Rhone-Poulenc Company)
ArCH(CH3)X + CO ArCH(CH3)COCOOH + ArCH(CH3)COOH + ArCH2CH2COOHCo2CO8, base
R'OH, H2O
X = Cl, Br, Ibase = Ca(OH)2, NaOH, LiOHmild condition: r.t. 0.2 MPa
CH2X+ CO + Ca(OH)2
5.0 MPa, 60 oC
Co2(CO)8, R'OH HCl OH
O
OOH
O+
R RR
X = F, Cl, Br, IR = H, X, CN, alkyl, aryl
![Page 33: Carbon Monoxide “Insertion” Siyu Ye 2008.1.25. 22 The term “insertion” is used to describe the process whereby an unsaturated moiety, which may or may](https://reader035.vdocument.in/reader035/viewer/2022062518/56649f255503460f94c3c08c/html5/thumbnails/33.jpg)
33
CH2ClCo(CO)4
- Co(CO)4+
Co(CO)4
O
OH
O
Co(CO)4
OH
OH
Co(CO)4
O
O
O
OH
CO
CO
OH-
OH-
Cassar, L. Ann. N. Y. Acad. Sci. 1980, 208, 333.Alper, H. Adv. Organomet. Chem. 1981, 19, 183.
![Page 34: Carbon Monoxide “Insertion” Siyu Ye 2008.1.25. 22 The term “insertion” is used to describe the process whereby an unsaturated moiety, which may or may](https://reader035.vdocument.in/reader035/viewer/2022062518/56649f255503460f94c3c08c/html5/thumbnails/34.jpg)
3434
ArX + 2CO + R2NH ArCOCONR2 + ArCONR2
PdCl2(PR3)2
50~100 oC, 1~4 MPa
Kobayashi, T.; Tanaka, M. J. Organomet. Chem. 1982, 233, C64.Ozawa, F.; Soyma, H.; Yamamoto, T.; Yamamoto, A. Tetrahedron Lett. 1982, 23, 3383.
Pd(0)
PdAr X
Pd XO
Ar
Pd XO
Ar CO
PdO
Ar
O
NR'2
Ar
O
O
NR'2
PdAr X
CO
PdArO
NR'2
Ar
O
NR'2
2R'2NH
R'2NH2X
CO
2R'2NH
R'2NH2X
Ozawa, F.; Sugimoto, T.; Yuasa, Y.; Santra, M.; Yamamoto, T.; Yamamoto, A. Organometallics 1984, 3, 683.
![Page 35: Carbon Monoxide “Insertion” Siyu Ye 2008.1.25. 22 The term “insertion” is used to describe the process whereby an unsaturated moiety, which may or may](https://reader035.vdocument.in/reader035/viewer/2022062518/56649f255503460f94c3c08c/html5/thumbnails/35.jpg)
35
R Br R
O
OH
O
R
O
OH+
Co2(CO)8, CO, base
3.6~5.0 MPa, 80 oC
R = Me 85% 10%
R = Ph 80% 7%
Ar-X ArCOCOOHCo2(CO)8
Me2SO4
Francalanci, F. ; Bencini, E.; Gardano, A.; Vincenti, M.; Foà, M. J. Organomet. Chem. 1986, 301, C27.
![Page 36: Carbon Monoxide “Insertion” Siyu Ye 2008.1.25. 22 The term “insertion” is used to describe the process whereby an unsaturated moiety, which may or may](https://reader035.vdocument.in/reader035/viewer/2022062518/56649f255503460f94c3c08c/html5/thumbnails/36.jpg)
3636
Content
1. Introduction
2. Acid Induced Carbonylation
3. Main Group Metal Induced Carbonylation
4. Transition Metal Induced Carbonylation
5. Conclusion
Background
Methanol Carbonylation
Hydroformylation
Double Carbonylation
![Page 37: Carbon Monoxide “Insertion” Siyu Ye 2008.1.25. 22 The term “insertion” is used to describe the process whereby an unsaturated moiety, which may or may](https://reader035.vdocument.in/reader035/viewer/2022062518/56649f255503460f94c3c08c/html5/thumbnails/37.jpg)
3737
Conclusion
Atom economical
Variety, wide application in industry and lab synthesis
Ni, Pd, Pt, Co, Rh catalysts, etc
Various influencing factors: substrate, catalyst, solvent, pressure,
temperature, additive, etc
![Page 38: Carbon Monoxide “Insertion” Siyu Ye 2008.1.25. 22 The term “insertion” is used to describe the process whereby an unsaturated moiety, which may or may](https://reader035.vdocument.in/reader035/viewer/2022062518/56649f255503460f94c3c08c/html5/thumbnails/38.jpg)
3838
Acknowledgment
Thanks for Prof. Yu.
Thanks for my group members.
Thanks for all the teachers and the students.
![Page 39: Carbon Monoxide “Insertion” Siyu Ye 2008.1.25. 22 The term “insertion” is used to describe the process whereby an unsaturated moiety, which may or may](https://reader035.vdocument.in/reader035/viewer/2022062518/56649f255503460f94c3c08c/html5/thumbnails/39.jpg)
39
Note
39
NR
R'
NR'R
Co(CO)4
Co(CO)4-
(OC)3CoNR'
R
CO
Co(CO)4-
(OC)4CoNR'
O
R
N
R'
O RCo(CO)4-
Co2(CO)8
CO
R = alkyl
NR'
Co(CO)4
Co(CO)4-
NR'
Co(CO)4
Co(CO)4-
![Page 40: Carbon Monoxide “Insertion” Siyu Ye 2008.1.25. 22 The term “insertion” is used to describe the process whereby an unsaturated moiety, which may or may](https://reader035.vdocument.in/reader035/viewer/2022062518/56649f255503460f94c3c08c/html5/thumbnails/40.jpg)
4040
X PdXLnPdXLn
O
OPdXLn
OPdXLn
O ONu
O
PdLn CO
NuCO
cyclicacylmetalation
I
OSiR3 OSiR3
OCOOMe
75 %, trans/cis = 3:1
PdCl2(PPh3)2, MeOH
15 bar CO, 100 oC
![Page 41: Carbon Monoxide “Insertion” Siyu Ye 2008.1.25. 22 The term “insertion” is used to describe the process whereby an unsaturated moiety, which may or may](https://reader035.vdocument.in/reader035/viewer/2022062518/56649f255503460f94c3c08c/html5/thumbnails/41.jpg)
4141
[Rh]
[Rh] Ar
[Rh] Ar
O
[Rh]
R
R
O Ar
R R
ArOO
[Rh]
O
RR
O[Rh]Ar
O
RR
OAr
ArB(OH)2
CO
R
R
CO
H+
R
R
B(OH)2
R'
O
R'
RR
O
[Rh(cod)Cl]2 20 atm CO
toluene80 oC,16 h
+
![Page 42: Carbon Monoxide “Insertion” Siyu Ye 2008.1.25. 22 The term “insertion” is used to describe the process whereby an unsaturated moiety, which may or may](https://reader035.vdocument.in/reader035/viewer/2022062518/56649f255503460f94c3c08c/html5/thumbnails/42.jpg)
4242
MeR
Rh
MeR
CORh
OMe
R
RhO
MeR
O
MeR
O
MeMeR
CO, Rh(I)
oxidative addition
CO insertion
isomerization reductiveelimination
-carbonelimination
1
23
4
52
Me
BnO
O
MeMe
BnOCO+
5 mol% [Rh(cod)Cl]2 10 mol% DPPP
p-xylene130 oC, 2.5 h
(1 atm)
84 %