Group Meeting in David’s Group
Vinyl Epoxides in Organic Synthesis
Reporter: Leifeng Wang
Supervisor: David Zhigang Wang
2014-06-05
Contents
• Background
• Synthesis of Vinyl Epoxides
• Reactions of Vinyl Epoxides
1) Strategy A: From Dienes
1) Nucleophilic Openings
2) Strategy B: From Epoxy
2) Eliminative Ring-Opening Reactions
3) Rearrangements
Aldehydes/Ketones
4) Radical Reactions
3) Strategy C: From Enone/Enal
4) Strategy D: From Aldehydes
5) Cycloadditions and Formal
Cycloadditions
• Summary
• Acknowledgment
2
Background
3
Contents
• Background
• Synthesis of Vinyl Epoxides
• Reactions of Vinyl Epoxides
1) Strategy A: From Dienes
1) Nucleophilic Openings
2) Strategy B: From Epoxy
2) Eliminative Ring-Opening Reactions
3) Rearrangements
Aldehydes/Ketones
4) Radical Reactions
3) Strategy C: From Enone/Enal
4) Strategy D: From Aldehydes
5) Cycloadditions and Formal
Cycloadditions
• Summary
• Acknowledgment
4
Synthesis of Vinyl Epoxides
5
Strategy A: From Dienes
More Electro-Deficient Double Bond
More Electro-Rich Double Bond
Directed Group
Alvarez-Manzaneda, E.; Chahboun, R.; Alvarez, E.; Jose Cano, M.; Haidour, A.; Alvarez-Manzaneda, R. n. Org. Lett. 2010, 12, 4450.
Liu, X.; Li, Y.; Wang, G.; Chai, Z.; Wu, Y.; Zhao, G. Tetrahedron: Asymmetry 2006, 17, 750.
6
Jogireddy, R.; Maier, M. E. J. Org. Chem. 2006, 71, 6999.
Strategy B: From Epoxy Aldehydes/Ketones
Olefination by Wittig-Type Reactions
Chandrasekhar, S.; Parida, B. B.; Rambabu, C. J. Org. Chem. 2008, 73, 7826.
Olefination by Aldol-Type Condensations
Jung, M. E.; Berliner, J. A.; Koroniak, L.; Gugiu, B. G.; Watson, A. D. Org. Lett. 2008, 10, 4207.
7
Strategy C: From Enone/Enal
Corey-Chaykovsky Epoxidation
Piccinini, A.; Kavanagh, S. A.; Connon, S. J. Chem. Commun. 2012, 48, 7814.
Darzen-Type Reactions
Gadaj, A.; Jonczyk, A. Synthesis 2007, 75.
8
Strategy D: From Aldehydes
Corey-Chaykovsky Epoxidation
Davoust, M.; Briere, J.-F.; Metzner, P. Org. Biomol. Chem. 2006, 4, 3048
via Halohydrin-Type Intermediates
Kang, B.; Britton, R. Org. Lett. 2007, 9, 5083.
9
Contents
• Background
• Synthesis of Vinyl Epoxides
• Reactions of Vinyl Epoxides
1) Strategy A: From Dienes
1) Nucleophilic Ring Openings
2) Strategy B: From Epoxy
2) Rearrangements
Aldehydes/Ketones
3) Radical Reactions
3) Strategy C: From Enone/Enal
4) Strategy D: From Aldehydes
4) Cycloadditions and Formal
Cycloadditions
• Summary
• Acknowledgment
10
Nucleophilic Ring Openings
11
Nucleophilic Ring Openings—Nitrogen Nucleophiles
Evans, D. A.; Campos, K. R.; Tedrow, J. S.; Michael, F. E.; Gagne,M.R. J. Am. Chem. Soc. 2000, 122, 7905.
Lindstrom, U. M.; Olofsson, B.; Somfai, P. Tetrahedron Lett. 1999, 40, 9273.
Righi, G.; Manni, L. S.; Bovicelli, P.; Pelagalli, R. Tetrahedron Lett. 2011, 52, 3895.
12
Nucleophilic Ring Openings—Nitrogen Nucleophiles
Chandrasekhar, S.; Parida, B. B.; Rambabu, C. J. Org. Chem. 2008, 73, 7826.
13
Yaragorla, S.; Muthyala, R. Tetrahedron Lett. 2010, 51, 467.
Nucleophilic Ring Openings—Oxygen Nucleophiles
Gomez, A. M.; Pedregosa, A.; Uriel, C.; Valverde, S.; Lopez, J. C. Eur. J. Org. Chem. 2010, 5619.
14
Buchanan, G. S.; Cole, K. P.; Tang, Y.; Hsung, R. P. J. Org. Chem. 2011, 76, 7027.
Nucleophilic Ring Openings—Oxygen Nucleophiles
Yu, X.-Q.; Hirai, A.; Miyashita, M. Chem. Lett. 2004, 33, 764.
Uchida, K.; Yokoshima, S.; Kan, T.; Fukuyama, T. Org. Lett. 2006, 8, 5311.
15
Nucleophilic Ring Openings—Oxygen Nucleophiles
Nicolaou, K. C.; Nakamura, T. M. B. T. J. Am. Chem. Soc. 2011, 133, 220.
Nicolaou, K. C.; Seo, J. H.; Nakamura, T.; Aversa, R. J. J. Am. Chem. Soc. 2011, 133, 214.
16
Fukui, H.; Shiina, I. Org. Lett. 2008, 10, 3153.
Nucleophilic Ring Openings—Sulfur Nucleophiles
Evans, D. A.; Campos, K. R.; Tedrow, J. S.; Michael, F. E.; Gagne,M.R. J. Am. Chem. Soc. 2000, 122, 7905.
17
Fedorov, A.; Fu, C.; Linden, A.; Heimgartner, H. Eur. J. Org. Chem. 2005, 1613.
Nucleophilic Ring Openings—Halide Nucleophiles
Hunter, L.; Kirsch, P.; Slawin, A. M. Z.; O’Hagan, D. Angew. Chem. Int. Ed. 2009, 48, 5457.
Murakami, T.; Shimizu, T.; Taguchi, K. Tetrahedron 2000, 56, 533.
18
Nucleophilic Ring Openings—Halide Nucleophiles
Usami, Y.; Ohsugi, M.; Mizuki, K.; Ichikawa, H.; Arimoto, M. Org. Lett. 2009, 11, 2699.
Buchanan, G. S.; Cole, K. P.; Tang, Y.; Hsung, R. P. J. Org. Chem. 2011, 76, 7027.
19
Nucleophilic Ring Openings—Hydride Nucleophiles
Gowrisankar, P.; Pujari, S. A.; Kaliappan, K. P. Chem. Eur. J. 2010, 16, 5858.
20
Ma, K.; Zhang, C.; Liu, M.; Chu, Y.; Zhou, L.; Hu, C.; Ye, D. Tetrahedron Lett. 2010, 51, 1870.
Nucleophilic Ring Openings—Carbon Nucleophiles
Friedel-Crafts-Type Reactions
Ono, M.; Suzuki, K.; Akita, H. Tetrahedron Lett. 1999, 40, 8223.
Alkenes
Myers, A. G.; Siu, M. Tetrahedron 2002, 58, 6397.
Enolate
21
Lovchik, M. A.; Frater, G.; Goeke, A.; Hug, W. Chem. Biodiversity 2008, 5, 126.
Nucleophilic Ring Openings—Carbon Nucleophiles
Mahapatra, S.; Carter, R. G. Org. Biomol. Chem. 2009, 7, 4582.
Xie, X.; Yue, G.; Tang, S.; Huo, X.; Liang, Q.; She, X.; Pan, X. Org. Lett. 2005, 7, 4057.
22
Di Bussolo, V.; Caselli, M.; Romano, M. R.; Pineschi, M.; Crotti, P. J. Org. Chem. 2004, 69, 8702.
Rearrangements
Pericyclic Reactions
Boyd, D. R.; Sharma, N. D.; Llamas, N. M.; O’Dowd, C. R.; Allen, C. C. R. Org. Biomol. Chem. 2007, 5, 2267.
Meinwald Rearrangements
Deng, X.-M.; Sun, X.-L.; Tang, Y. J. Org. Chem. 2005, 70, 6537
Ring Expansion Rearrangements
23
Brichacek, M.; Batory, L. A.; Njardarson, J. T. Angew. Chem., Int. Ed. 2010, 49, 1648.
Radical Reactions
Reactions of Alkoxy Radicals
24
Ogawa, Y.; Kuroda, K.; Mukaiyama, T. Chem. Lett. 2005, 34, 698.
Radical Reactions
Reactions of Carbon Radicals
Feldman, K. S.; Fisher, T. E. Tetrahedron 1989, 45, 2969.
Reactions of Allylic Radicals
Yadav, J. S.; Srinivas, D.; Shekharam, T. Tetrahedron Lett. 1994, 35, 3625.
25
Cycloadditions and Formal Cycloadditions
26
Cycloadditions and Formal Cycloadditions
(3 + 2) Cycloadditions
Yıldırım, M.; Durust, Y. Tetrahedron 2011, 67, 3209.
Trost, B. M.; Angle, S. R. J. Am. Chem. Soc. 1985, 107, 6123
27
Cycloadditions and Formal Cycloadditions
(4 + 2) Cycloadditions
Pale, P.; Bouquant, J.; Chuche, J.; Carrupt, P. A.; Vogel, P. Tetrahedron 1994, 50, 8035.
(4 + 3) Cycloadditions
Liu, L. L.; Chiu, P. Chem. Commun. 2011, 47, 3416
(5 + 2) Cycloadditions
28
Feng, J.-J.; Zhang, J. J. Am. Chem. Soc. 2011, 133, 7304.
Summary
29
Thank you for your attention!
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51