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Carbon Monoxide “Insertion”
Siyu Ye
2008.1.25
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).
Anderson, G. K.; Cross, R. J. Acc. Chem. Res. 1984,17, 67.
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Content
1.
Introduction
2.
Acid Induced Carbonylation
3.
Main Group Metal Induced Carbonylation
4.
Transition Metal Induced Carbonylation
5.

Background

Methanol Carbonylation

Hydroformylation

Double Carbonylation
Conclusion
3
Content
1.
Introduction
2.
Acid Induced Carbonylation
3.
Main Group Metal Induced Carbonylation
4.
Transition Metal Induced Carbonylation
5.

Background

Methanol Carbonylation

Hydroformylation

Double Carbonylation
Conclusion
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The CO Molecule
Molecular Orbital of Carbon Monoxide
C+O-, electronegativity
LUMO
C-O+, a low dipole moment of 0.112 D
HOMO
Henrici-Olivé, G.; Olivé, S. The Chemistry of the Catalyzed
Hydrogenation of Carbon Monoxide; Springer-Verlag: Berlin,
Heidelberg, New York, Tokyo, 1984; p 23.
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Migratory Insertion
Which is more appropriate?
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alkyl migration
Calderazzo, F. Angew. Chem., Int. Ed. 1977, 16, 299.
CO migration
Brunner, H.; Vogt, H. Angew. Chem., Int. Ed. 1981, 20, 405.
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Influence Factors
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
Cavell, K. J. Coord. Chem. Rev. 1996, 155, 209.
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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
Henrici-Olivé, G.; Olivé, S. The Chemistry of the Catalyzed Hydrogenation of Carbon Monoxide;
Springer-Verlag: Berlin, Heidelberg, New York, Tokyo, 1984; p 79.
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Content
1.
Introduction
2.
Acid Induced Carbonylation
3.
Main Group Metal Induced Carbonylation
4.
Transition Metal Induced Carbonylation
5.

Background

Methanol Carbonylation

Hydroformylation

Double Carbonylation
Conclusion
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Acid Induced Carbonylation
Koch carbonylation
Farcasiu, D.; Schlosberg, R. H. J. Org. Chem. 1982, 47, 151.
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Content
1.
Introduction
2.
Acid Induced Carbonylation
3.
Main Group Metal Induced Carbonylation
4.
Transition Metal Induced Carbonylation
5.

Background

Methanol Carbonylation

Hydroformylation

Double Carbonylation
Conclusion
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Li Induced Carbonylation
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.
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Mg Induced Carbonylation
Sprangers, W. J. J. M.; Louw, R. J. Chem. Soc., Perkin Trans. 2 1976, 1895.
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Al Induced Carbonylation
Mason, M. R.; Song, B.; Kirschbaum, K. J. Am. Chem. Soc. 2004, 126, 11812.
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Content
1.
Introduction
2.
Acid Induced Carbonylation
3.
Main Group Metal Induced Carbonylation
4.
Transition Metal Induced Carbonylation
5.

Background

Methanol Carbonylation

Hydroformylation

Double Carbonylation
Conclusion
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Transition Metal Induced Carbonylation
Chiusoli, G. P. Acc. Chem. Res. 1973, 6, 422.
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Schoenberg, A.; Bartoletti, I.; Heck, R. F. J. Org. Chem. 1974, 39, 23.
Heck, R. F. J. Am. Chem. Soc. 1963, 85, 2013.
Reppe process
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CO-to-C—X Insertion
Heck, R. F. J. Am. Chem. Soc. 1963, 85, 1460.
Wang, M. D.; Alper, H. J. Am. Chem. Soc. 1992, 114, 7018.
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Pauson-Khand Reaction
Paquette, L. A.; Borrelly, S. J. Org. Chem. 1995, 60, 6912.
Tang, Y.; Deng, L.; Zhang, Y.; Dong, G.; Chen, J.; Yang, Z. Org. Lett. 2005, 7, 1657.
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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.
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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.
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Peng, C.; Cheng, J.; Wang, J. J. Am. Chem. Soc. 2007, 129, 8708.
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.
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Content
1.
Introduction
2.
Acid Induced Carbonylation
3.
Main Group Metal Induced Carbonylation
4.
Transition Metal Induced Carbonylation
5.

Background

Methanol Carbonylation

Hydroformylation

Double Carbonylation
Conclusion
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Methanol Carbonylation
Monsanto process
Forster, D. J. Am. Chem. Soc. 1976, 98, 846.
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殷元骐 主编,《羰基合成化学》, p 167.
Hydroformylation
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 ratio
100 ℃, p(CO) from 0.25 MPa to 9.0 MPa,
n/iso from 1.6 to 4.4
high p(CO), high p(H2)
殷元骐 主编,《羰基合成化学》, p 4.
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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.
TPPTS = P(m-C6H4SO3Na)3
Nair, V. S. et. al. Rec. Adv. Basic Appl. Aspects Industr. Catal. 1998, 113, 529.
Smith, W. E. et. al. In Catalysis of Organic Reactions; Augustine, R. L., Ed.; Dekker: New York, 1985; p 151.
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Kranemann, C. L.; Eilbracht, P. Synthesis 1998, 71.
Roggenbuck, R.; Eilbracht, P. Tetrahedron Lett. 1999, 40, 7455.
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Asymmetric Hydroformylation
Difficulties : 1. High regioselectivity
2. High enantioselectivity
3. No racemization of aldehyde
Sakai, N.; Mano, S.; Nozaki, K.; Takaya, H. J. Am. Chem. Soc. 1993, 115, 7033.
Breit, B. Acc. Chem. Res. 2003, 36, 264.
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Diastereoselective Hydroformylation
Breit, B. Angew. Chem., Int. Ed. 1996, 35, 2835.
Breit, B.; Zahn, S. K. Angew. Chem., Int. Ed. 1999, 38, 969.
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Double Carbonylation
(Rhone-Poulenc Company)
殷元骐 主编,《羰基合成化学》
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Cassar, L. Ann. N. Y. Acad. Sci. 1980, 208, 333.
Alper, H. Adv. Organomet. Chem. 1981, 19, 183.
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Kobayashi, T.; Tanaka, M. J. Organomet. Chem. 1982, 233, C64.
Ozawa, F.; Soyma, H.; Yamamoto, T.; Yamamoto, A. Tetrahedron Lett. 1982, 23, 3383.
Ozawa, F.; Sugimoto, T.; Yuasa, Y.; Santra, M.; Yamamoto, T.; Yamamoto, A. Organometallics 1984, 3, 683.
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Francalanci, F. ; Bencini, E.; Gardano, A.; Vincenti, M.; Foà, M. J. Organomet. Chem. 1986, 301, C27.
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Content
1.
Introduction
2.
Acid Induced Carbonylation
3.
Main Group Metal Induced Carbonylation
4.
Transition Metal Induced Carbonylation
5.

Background

Methanol Carbonylation

Hydroformylation

Double Carbonylation
Conclusion
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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
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Acknowledgment
Thanks for Prof. Yu.
Thanks for my group members.
Thanks for all the teachers and the students.
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Note
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