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C-H Insertion of Rhodium-Carbene Using Diazo Compounds

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* Metal-Carbenes Metal Carbenes in Organic Synthesis; D rwald, F. G., Ed.; Wiley-VCH: Weinheim, 1999. * Synthesis of Diazo Compounds Doyle, M. P.; McKervey, ... – PowerPoint PPT presentation

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Title: C-H Insertion of Rhodium-Carbene Using Diazo Compounds


1
C-H Insertion of Rhodium-Carbene Using Diazo
Compounds
  • Presented by Pascal Cérat
  • Litterature Meeting
  • 6 april 2010

2
Carbenes
Metal Carbenes in Organic Synthesis Dörwald, F.
G., Ed. Wiley-VCH Weinheim, 1999. Bourissou,
D. Guerret, O. Gabbaï, F. P. Bertrand, G.
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3
Metal-Carbenes
3
Metal Carbenes in Organic Synthesis Dörwald, F.
G., Ed. Wiley-VCH Weinheim, 1999.
4
Synthesis of Diazo Compounds
4
Doyle, M. P. McKervey, M. A. Ye, T. Modern
Catalytic Methods for Organic Synthesis with
Diazo Compounds Wiley-VCH New York, 1998.
5
Reactivity of Diazo Compounds
5
Doyle, M. P. McKervey, M. A. Ye, T. Modern
Catalytic Methods for Organic Synthesis with
Diazo Compounds Wiley-VCH New York,
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Zhou, L. Chem. Rev. 2010, 110, 704.
6
C-H Insertion by Carbenes
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Introduction of Rhodium C-H Insertion
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Propreties of Rhodium
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C-H Insertion vs C-H Activation
9
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General Mechanism of C-H Insertion
10
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General Mechanism of C-H Insertion
11
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Intramolecular C-H insertion Regioselectivity
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Regioselectivity Modulated by Electronic Effect
of the C-H
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Changing the a-Group of the Diazo
14
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Impact of the Ligands on Regioselectivity
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Impact of the Ligands on Chemioselectivity
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17
Influence of Ligand on Dirhodium(II) Carbene
17
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Diastereoselectivity in C-H insertion
18
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Chiral Dirhodium Catalyst in C-H Insertion
19
Doyle, M. P. Duffy, R. Ratnikov, M. Zhou, L.
Chem. Rev. 2010, 110, 704.
20
Carboxylates in Intramolecular C-H Insertion
20
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Carboxylates in Intramolecular C-H Insertion
21
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Carboxylates in Intramolecular C-H Insertion
22
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23
Carboxamidates in Intramolecular C-H Insertion
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23
24
Understanding the Utility of Carboxamidate as
Ligands
24
Doyle, M. P. Oeveren, A. v. Westrum, L. J.
Protopopova, M. N. Clayton, T. W., Jr. J. Am.
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Nakamura, E. Adv. Synth. Catal. 2003, 345,
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Zhou, L. Chem. Rev. 2010, 110, 704.
25
Understanding the Utility of Carboxamidate as
Ligands
25
Doyle, M. P. Oeveren, A. v. Westrum, L. J.
Protopopova, M. N. Clayton, T. W., Jr. J. Am.
Chem. Soc. 1991, 113, 8982. Yoshikai, N.
Nakamura, E. Adv. Synth. Catal. 2003, 345,
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Zhou, L. Chem. Rev. 2010, 110, 704.
26
Understanding the Utility of Carboxamidate as
Ligands
26
Doyle, M. P. Morgan, J. P. Fettinger, J. C.
Zavalij, P. Y. Colyer, J. T. Timmons, D. J.
Carbucci, M. D. J. Org. Chem. 2005, 70,
5291. Doyle, M. P. Duffy, R. Ratnikov, M.
Zhou, L. Chem. Rev. 2010, 110, 704.
27
Diastereoselectivity with Dirhodium Carboxamidates
27
Doyle, M. P. Morgan, J. P. Fettinger, J. C.
Zavalij, P. Y. Colyer, J. T. Timmons, D. J.
Carbucci, M. D. J. Org. Chem. 2005, 70,
5291. Doyle, M. P. Duffy, R. Ratnikov, M.
Zhou, L. Chem. Rev. 2010, 110, 704.
28
Use of Othometalated Aryl Phosphine Ligands
28
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M. Perez-Prieto, J. Organometallics 2001, 20,
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29
Intermolecular C-H Insertion Reactions
29
Doyle, M. P. Duffy, R. Ratnikov, M. Zhou, L.
Chem. Rev. 2010, 110, 704.
30
Aryldiazoacetate in Intermolecular C-H Insertion
Reactions
30
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Duffy, R. Ratnikov, M. Zhou, L. Chem. Rev.
2010, 110, 704.
31
Aryldiazoacetate in Intermolecular C-H Insertion
Reactions
Davies, H. M. L. Hansen, T. Hopper, D. W.
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Beckwith, R. E. J. Antoulinakis, E. G. Jin, Q.
J. Org. Chem. 2003, 68, 6126. Doyle, M. P.
Duffy, R. Ratnikov, M. Zhou, L. Chem. Rev.
2010, 110, 704.
31
32
Aryldiazoacetate in Intermolecular C-H Insertion
Reactions
32
Davies, H. M. L. Venkatarmani, C. Angew. Chem.
Int. Ed. 2002, 41, 2197. Davies, H. M. L.
Beckwith, R. E. J. Antoulinakis, E. G. Jin, Q.
J. Org. Chem. 2003, 68, 6126.
33
Aryldiazoacetate in Intermolecular C-H Insertion
Reactions
33
Davies, H. M. L. Hedley, S. J. Bohall, B.R. J.
Org. Chem. 2005, 70, 10737.
34
Vinyldiazoacetate in Intermolecular C-H Insertion
Reactions
34
Davies, H. M. L. Stafford, D. G. Hansen, T.
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Manning, J. R. Nature 2008, 451, 417.
35
Intermolecular C-H Insertion Cope Rearrangement
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35
36
Intermolecular C-H Insertion Cope Rearrangement
36
Davies, H. M. L. Jin, Q. J. Am. Chem. Soc. 2004,
126, 10862. Davies, H. M. L. Nikolai, J. Org.
Biomol. Chem. 2005, 3, 4176.
37
Intermolecular C-H Insertion Cope Rearrangement
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37
38
Intermolecular C-H Insertion Cope Rearrangement
Davies, H. M. L. Walji, A. M. Angew. Chem. Int.
Ed. 2005, 44, 1733. Davies, H. M. L. Nikolai, J.
Org. Biomol. Chem. 2005, 3, 4176. Davies, H. M.
L. Dai, X. Long, M. S. J. Am. Chem. Soc. 1996,
128, 2485. Davies, H. M. L. Manning, J. R.
Nature 2008, 451, 417.
38
39
Conclusion
39
Davies, H. M. L. Manning, J. R. Nature 2008,
451, 417. Doyle, M. P. Duffy, R. Ratnikov, M.
Zhou, L. Chem. Rev. 2010, 110, 704.
40
Conclusion
40
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