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Transcript of Carbon Monoxide “Insertion” Siyu Ye 2008.1.25. 22 The term “insertion” is used to describe...
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 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
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
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
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
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?
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
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
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
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
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
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
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
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
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.
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
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
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
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
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
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
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)
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.
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
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
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
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)
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.
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.
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
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
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
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.
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.
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.
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
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
3838
Acknowledgment
Thanks for Prof. Yu.
Thanks for my group members.
Thanks for all the teachers and the students.
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-
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
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
+
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 %