When Asymmetric Aminocatalysis Meets the Vinylogy Principle
Event details
| Date | 20.03.2013 |
| Hour | 17:15 › 18:30 |
| Speaker |
Prof. Paolo Melchiorre, ICIQ - Institute of Chemical Research of Catalonia, Tarragona (Spain) ICREA - Institució Catalana de Recerca i Estudis Avançats, Barcelona (Spain) |
| Location | |
| Category | Conferences - Seminars |
When Asymmetric Aminocatalysis Meets the Vinylogy Principle
Paolo Melchiorre
ICIQ - Institute of Chemical Research of Catalonia, Tarragona (Spain)
ICREA - Institució Catalana de Recerca i Estudis Avançats, Barcelona (Spain)
e-mail: [email protected]
Asymmetric aminocatalysis has greatly expanded the chemist’s ability to stereoselectively functionalise unmodified carbonyl compounds. The field has coalesced around two pioneering studies, , which recognized that chiral amines could activate carbonyl compounds according to fundamental and general reactivity concepts: the LUMO-lowering effect, which is the underlying activation principle of iminium ion catalysis,2 and the HOMO-raising effect inherent to enamine catalysis.3 Those activation modes account for the functionalisation of carbonyls at their and positions, respectively. The successful marriage of these reactivity concepts to the principle of vinylogy has recently led to the development of novel aminocatalytic activation modes, which allow for the direct, stereoselective, and site-selective functionalization of unsaturated carbonyls at remote positions, such as the and even the positions.
Here, some recent contributions from our laboratories are presented.
Figure 1. Established activation modes in aminocatalysis and the vinylogous iminium ion strategy
. (a) List, B.; Angew. Chem., Int. Ed. 2010, 49, 1730-1734. (b) Barbas, C. F. III; Angew. Chem., Int. Ed. 2008, 47, 42-47. (c) Melchiorre, P.; Marigo, M.; Carlone, A.; Bartoli, G. Angew. Chem., Int. Ed. 2008, 47, 6138-6171.
. Ahrendt, K. A.; Borths, C. J.; MacMillan, D. W. C. J. Am. Chem. Soc. 2000, 122, 4243–4244.
. List, B.; Lerner, R. A.; Barbas C. F. III, J. Am. Chem. Soc. 2000, 122, 2395–2396.
. a) Fuson, R. C. Chem. Rev. 1935, 16, 1–27; b) Arceo, E.; Melchiorre, P. Angew. Chem., Int. Ed. 2012, 51, 5290-5292.
. For the seminal study: S. Bertelsen, M. Marigo, S. Brandes, P. Dinér, K. A. Jørgensen, J. Am. Chem. Soc. 2006, 128, 12973–12980.
. For the landmark report: Jia, Z. J.,Jiang, H.; Li, J.-L.; Gschwend, B.; Li, Q.-Z.; Yin, X.; Grouleff, J.; Chen, Y.-C. Jørgensen, K. A.; J. Am. Chem. Soc. 2011, 133, 5053–5061.
. (a) Bencivenni, G.; Galzerano, P.; Mazzanti, A.; Bartoli, G.; Melchiorre, P. Proc. Natl. Acad. Sci. U.S.A., 2010, 107, 20642–20647. (b) Bergonzini, G.; Vera, S.; Melchiorre, P. Angew. Chem., Int. Ed. 2010, 49, 9685–9688. (c) Xu, T.; Liu, Y.; Melchiorre, P. Angew. Chem., Int. Ed. 2012, 51, 6439-6442.
Paolo Melchiorre
ICIQ - Institute of Chemical Research of Catalonia, Tarragona (Spain)
ICREA - Institució Catalana de Recerca i Estudis Avançats, Barcelona (Spain)
e-mail: [email protected]
Asymmetric aminocatalysis has greatly expanded the chemist’s ability to stereoselectively functionalise unmodified carbonyl compounds. The field has coalesced around two pioneering studies, , which recognized that chiral amines could activate carbonyl compounds according to fundamental and general reactivity concepts: the LUMO-lowering effect, which is the underlying activation principle of iminium ion catalysis,2 and the HOMO-raising effect inherent to enamine catalysis.3 Those activation modes account for the functionalisation of carbonyls at their and positions, respectively. The successful marriage of these reactivity concepts to the principle of vinylogy has recently led to the development of novel aminocatalytic activation modes, which allow for the direct, stereoselective, and site-selective functionalization of unsaturated carbonyls at remote positions, such as the and even the positions.
Here, some recent contributions from our laboratories are presented.
Figure 1. Established activation modes in aminocatalysis and the vinylogous iminium ion strategy
. (a) List, B.; Angew. Chem., Int. Ed. 2010, 49, 1730-1734. (b) Barbas, C. F. III; Angew. Chem., Int. Ed. 2008, 47, 42-47. (c) Melchiorre, P.; Marigo, M.; Carlone, A.; Bartoli, G. Angew. Chem., Int. Ed. 2008, 47, 6138-6171.
. Ahrendt, K. A.; Borths, C. J.; MacMillan, D. W. C. J. Am. Chem. Soc. 2000, 122, 4243–4244.
. List, B.; Lerner, R. A.; Barbas C. F. III, J. Am. Chem. Soc. 2000, 122, 2395–2396.
. a) Fuson, R. C. Chem. Rev. 1935, 16, 1–27; b) Arceo, E.; Melchiorre, P. Angew. Chem., Int. Ed. 2012, 51, 5290-5292.
. For the seminal study: S. Bertelsen, M. Marigo, S. Brandes, P. Dinér, K. A. Jørgensen, J. Am. Chem. Soc. 2006, 128, 12973–12980.
. For the landmark report: Jia, Z. J.,Jiang, H.; Li, J.-L.; Gschwend, B.; Li, Q.-Z.; Yin, X.; Grouleff, J.; Chen, Y.-C. Jørgensen, K. A.; J. Am. Chem. Soc. 2011, 133, 5053–5061.
. (a) Bencivenni, G.; Galzerano, P.; Mazzanti, A.; Bartoli, G.; Melchiorre, P. Proc. Natl. Acad. Sci. U.S.A., 2010, 107, 20642–20647. (b) Bergonzini, G.; Vera, S.; Melchiorre, P. Angew. Chem., Int. Ed. 2010, 49, 9685–9688. (c) Xu, T.; Liu, Y.; Melchiorre, P. Angew. Chem., Int. Ed. 2012, 51, 6439-6442.
Practical information
- General public
- Free
Organizer
- Organic Chemistry Seminar hosted by Prof. Nicolai Cramer
[email protected]
Contact
- Prof. Nicolai Cramer
[email protected]