C-H Insertion of Rhodium-Carbene Using Diazo Compounds - PowerPoint PPT Presentation

1 / 40
About This Presentation
Title:

C-H Insertion of Rhodium-Carbene Using Diazo Compounds

Description:

* 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

Number of Views:563
Avg rating:3.0/5.0
Slides: 41
Provided by: Pasc70
Category:

less

Transcript and Presenter's Notes

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.
Chem. Rev. 2000, 100, 39.
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,
1998. Doyle, M. P. Duffy, R. Ratnikov, M.
Zhou, L. Chem. Rev. 2010, 110, 704.
6
C-H Insertion by Carbenes
Doering, W. v. E. Buttery, R. G. Laughlin, R.
G. Chaudhuri, N. J. Am. Chem. Soc. 1956, 78,
3224. Doering, W. v. E. Knox, L. H. J. Am.
Chem. Soc. 1956, 78, 4947. Greuter, F. Kalvoda,
J. Jeger, O. Proc. Chem. Soc. 1958, 348. Yates,
P. Danishefsky, S. J. Am. Chem. Soc. 1962, 84,
879. Doyle, M. P. Duffy, R. Ratnikov, M. Zhou,
L. Chem. Rev. 2010, 110, 704.
6
7
Introduction of Rhodium C-H Insertion
Demonceau, A. Noels, A. F. Hubert, A. J.
Teyssié, P. J. Chem. Soc. Chem. Commun. 1981,
688. Demonceau, A. Noels, A. F. Hubert, A. J.
Teyssié, P. Bull. Soc. Chim. Belg. 1984, 93,
945. Wenkert, E. Davis, L. L. Mylari, B. L.
Solomon, M. F. Da Silva, R. R. Shulman, S.
Warnet, R. J. J. Org. Chem. 1982, 47,
3242. Doyle, M. P. Duffy, R. Ratnikov, M.
Zhou, L. Chem. Rev. 2010, 110, 704.
7
8
Propreties of Rhodium
8
Padwa, A. Austin, D. J. Angew. Chem. Int. Ed.
Engl. 1994, 33, 1797. Doyle, M. P. Duffy, R.
Ratnikov, M. Zhou, L. Chem. Rev. 2010, 110, 704.
9
C-H Insertion vs C-H Activation
9
Davies, H. M. Manning, J. R. Nature 2008, 451,
417. Doyle, M. P. Duffy, R. Ratnikov, M. Zhou,
L. Chem. Rev. 2010, 110, 704.
10
General Mechanism of C-H Insertion
10
Nakamura, E. Yoshikai, N. Yamanaka, M. J. Am.
Chem. Soc. 2002, 124, 7181.
11
General Mechanism of C-H Insertion
11
Nakamura, E. Yoshikai, N. Yamanaka, M. J. Am.
Chem. Soc. 2002, 124, 7181.
12
Intramolecular C-H insertion Regioselectivity
12
Taber, D. F. Petty, E. H. J. Org. Chem. 1982,
47, 4808. Taber, D. H. Ruckle, R. E., Jr. J. Am.
Chem. Soc. 1986, 108, 7686.
13
Regioselectivity Modulated by Electronic Effect
of the C-H
13
Stork, G. Nakatani, K. Tet. Lett. 1988, 29,
2283. Spero, D. M. Adams, J. Tet. Lett. 1992,
33, 1143. Davies, H. M. Manning, J. R. Nature
2008, 451, 417.
14
Changing the a-Group of the Diazo
14
Yoon, C. H. Zaworotko, M. J. Moulton, B. Jung,
K. W. Org. Lett. 2001, 3, 3539. Gois, P. M. P.
Afonso, A. M. Eur. J. Org. Chem. 2003, 3798.
15
Impact of the Ligands on Regioselectivity
Doyle, M. P. Tauton, J. Pho, H. Q. Tet. Lett.
1989, 30, 5397. Doyle, M. P. Bagheri, V.
Pearson, M. M. Edwards, J. D. Tet. Lett. 1989,
30, 7001. Doyle, M. P. Westrum, L. J. Wolthuis,
W. N. E. See, M. M. Boone, W. P. Bagheri, V.
Pearson, M. M. J. Am. Chem. Soc. 1993, 115,
958. Padwa, A. Austin, D. J. Angew. Chem. Int.
Ed. Engl. 1994, 33, 1797.
15
16
Impact of the Ligands on Chemioselectivity
Padwa, A. Austin, D. J. Price, A. T. Semones,
M. A. Doyle, M. P. Protopopova, M. N.
Winchester, W. R. Tran, A. J. Am. Chem. Soc.
1993, 115, 8669. Estevan, F. Lahuerta, P.
Pérez-Prieto, J. Sanau, M. Stiriba, S.-E.
Ubeda, M. A. Organometallics 1997, 16,
880. Doyle, M. P. Duffy, R. Ratnikov, M. Zhou,
L. Chem. Rev. 2010, 110, 704.
16
17
Influence of Ligand on Dirhodium(II) Carbene
17
Lloret, J. Carbo, J. J. Bo, C. Lledos, A.
Pérez-Prieto, J. Organometallics 2008, 27, 2873.
18
Diastereoselectivity in C-H insertion
18
Taber, D. F. You, K. K. Rheingold, A. J. Am.
Chem. Soc. 1996, 118, 547.
19
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
Anada, M. Kitagaki, S. Hashimoto, S.
Heterocycles 2000, 52, 875.
21
Carboxylates in Intramolecular C-H Insertion
21
Anada, M. Kitagaki, S. Hashimoto, S.
Heterocycles 2000, 52, 875.
22
Carboxylates in Intramolecular C-H Insertion
22
Davies, H. M. Grazini, M. V. A. Aouad, E. Org.
Lett. 2001, 3, 1475. Saito, H. Oishi, H.
Kitagaki, S. Nakamura, S. Anada, M. Hashimoto,
S. 2002, 4, 3887. Reddy, R. P. Lee, G. H.
Davies, H. M. L. Org. Lett. 2006, 8, 3437.
23
Carboxamidates in Intramolecular C-H Insertion
Doyle, M. P. Oeveren, A. v. Westrum, L. J.
Protopopova, M. N. Clayton, T. W., Jr. J. Am.
Chem. Soc. 1991, 113, 8982. Doyle, M. P.
Dyatkhin, A. B. Roos, G. H. P. Canas, F.
Pierson, D. A. Basten, A. v. J. Am. Chem. Soc.
1994, 116, 4507. Doyle, M. P. Forbes, D. C.
Chem. Rev. 1998, 98, 911. Doyle, M. P. Duffy,
R. Ratnikov, M. Zhou, L. Chem. Rev. 2010, 110,
704.
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.
Chem. Soc. 1991, 113, 8982. Yoshikai, N.
Nakamura, E. Adv. Synth. Catal. 2003, 345,
1159. Doyle, M. P. Duffy, R. Ratnikov, M.
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,
1159. Doyle, M. P. Duffy, R. Ratnikov, M.
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
Estevan, F. Herbst, K. Lahuerta, P. Barberis,
M. Perez-Prieto, J. Organometallics 2001, 20,
950. Doyle, M. P. Duffy, R. Ratnikov, M. Zhou,
L. Chem. Rev. 2010, 110, 704.
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
Davies, H. M. L. Hansen, T. Churchill, M. R. J.
Am. Chem. Soc. 2000, 122, 3063. Doyle, M. P.
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.
Panaro, S. A. J. Am. Chem. Soc. 1999, 121,
6509. 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. 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.
Org. Lett. 1999, 1, 233. Davies, H. M. L.
Manning, J. R. Nature 2008, 451, 417.
35
Intermolecular C-H Insertion Cope Rearrangement
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. Davies, H. M. L.
Manning, J. R. Nature 2008, 451, 417.
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
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.
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
Write a Comment
User Comments (0)
About PowerShow.com