Cope Rearrangement

Atom Hopscotch:
Cascades Involving Catalysis and
Sigma-[3,3] Rearrangments
Reporter: Zhiyao Zhou
Supervisor: Prof. Luo
3/28/2014
Content
• Introduction
• Cope Rearrangement
• Claisen Rearrangement
• Cationic Hetero-Cope Rearrangement
• Summary
2
Content
• Introduction
• Cope Rearrangement
• Claisen Rearrangement
• Cationic Hetero-Cope Rearrangement
• Summary
3
Introduction
Sigma-[3,3]
Rearrangements
Catalysis
Various Cascade
Reactions
4
Content
• Introduction
• Cope Rearrangement
• Claisen Rearrangement
• Cationic Hetero-Cope Rearrangement
• Summary
5
Cope Rearrangement
• General Feature
Cope, A. C. et al. J. Am. Chem. Soc. 1940, 62, 441.
Grigg, R. et al. J. Chem. Soc. D, 1969, 99b.
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Cope Rearrangement
• Strain-Release Cope Rearrangement
– Metal Catalyzed Cyclopropanation + Cope
Davies, H. M. L. et al. Tetrahedron Lett. 1985, 26, 5659.
Davies, H. M. L. & Williams, C. M. et al. J. Am. Chem. Soc. 2009, 131, 8329.
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Cope Rearrangement
• Strain-Release Cope Rearrangement
– Alkyne Metathesis + Cope
. Padwa, A. et al. J. Org. Chem. 1995, 60, 53.
Montgomery, J. et al. J. Am. Chem. Soc. 2006, 128, 2609.
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Cope Rearrangement
• Strain-Release Cope Rearrangement
– Enyne Cycloisomerization + Cope
Chung, Y. K. et al. Angew. Chem. 2010, 122, 425.; Angew. Chem. Int. Ed. 2010, 49, 415.
Iwasawa, N. et al. J. Am. Chem. Soc. 2006, 128, 16500.
9
Cope Rearrangement
• Strain-Release Cope Rearrangement
– Cope + Norrish Type 1
Stoltz, B. M. et al. J. Am. Chem. Soc. 2003, 125, 13624.;
Stoltz, B. M. & Goddard III, W. A. et al. J. Am. Chem. Soc. 2004, 126, 24.
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Cope Rearrangement
• Strain-Release Cope Rearrangement
– Cyclobutane Strain Release Cope Rearrangement
Snapper, M. L. et al. J. Am. Chem. Soc. 2000, 122, 8071.;
Snapper, M. L. et al. J. Am. Chem. Soc. 1997, 119, 1478.
Kanematsu, K. et al. Tetrahedron 1995, 51, 3499.;
Kanematsu, K. et al. J. Am. Chem. Soc. 1989, 111, 5312.
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Cope Rearrangement
• Oxo Cope Rearrangement
– Classic Anionic Oxo-Cope Rearrangement
Huq, C. A. M. A. et al. Tetrahedron Lett. 2007, 48, 775.
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Cope Rearrangement
• Oxo Cope Rearrangement
– Combining Transition Metal Catalysis with Oxo-Cope
Leighton, J. L. et al. J. Org. Chem. 2003, 68, 1693.
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Cope Rearrangement
• Oxo Cope Rearrangement
– Combining Organocatalysis with Oxo-Cope
Bode, J. W. et al. J. Am. Chem. Soc. 2007, 129, 3520.
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Cope Rearrangement
• Other Cope Rearrangement
Kuehne, M. E. et al. J. Org. Chem. 1998, 63, 9427.;
Kuehne, M. E. et al. J. Org. Chem. 1997, 62, 7950.
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Content
• Introduction
• Cope Rearrangement
• Claisen Rearrangement
• Cationic Hetero-Cope Rearrangement
• Summary
16
Claisen Rearrangement
• Tandem Pericyclic Reaction
A. Nissen, W. Rebafka, W. Aquila, United States Patent 4288636, 09/08/, 1981.
M. Hiersemann, et al. Synlett. 2002, 1999.
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Claisen Rearrangement
• Tandem Pericyclic Reaction
– Cascade involving Johnson-Claisen Rearrangement
Chida, N. et al. Tetrahedron Lett. 2008, 49, 358.
Mulzer, J. et al. Angew. Chem. 1991, 103, 450.; Angew. Chem. Int. Ed. Engl. 1991, 30, 414.
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Claisen Rearrangement
• Claisen + Cyclization
Hii, K. K. (M.) et al. Chem. Commun. 2008, 2325.
Saito, A. & Hanzawa, Y. et al. J. Org. Chem. 2009, 74, 1517.
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Claisen Rearrangement
• Claisen + Cyclization
– Gold Catalyzed Propargyl Ester Rearrangement
F. Gagosz, et al. Org. Lett. 2006, 8, 1957.
L. Zhang, et al. J. Am. Chem. Soc. 2006, 128, 1442.
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Claisen Rearrangement
• Metal Catalyzed Coupling/Isomerization + Claisen
Buchwald, S. L. et al. J. Am. Chem. Soc. 2003, 125, 4978.
Wood, J. L. et al. J. Am. Chem. Soc. 1997, 119, 9641.
Wood, J. L. et al. Org. Lett. 1999, 1, 371.
Wood, J. L. et al. J. Org. Chem. 2001, 66, 7025.
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Claisen Rearrangement
• Metal Catalyzed Coupling/Isomerization + Claisen
– Metallo-Claisen Rearrangement
Trost, B. M. et al J. Am. Chem. Soc. 1990, 112, 7809.
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Claisen Rearrangement
• Metal Catalyzed Coupling/Isomerization + Claisen
– Bamford-Stevens/Claisen Rearrangement
Stoltz, B. M. et al J. Am. Chem. Soc. 2002, 124, 12426.
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Claisen Rearrangement
• Metal Catalyzed Isomerization + Claisen
– From Allylic Ether to Eno Ether
Salomon, R. G. et al. J. Org. Chem. 1977, 42, 3360.
Swenton, J. S. et al. J. Org. Chem. 1991, 56, 6156.
Tanaka, K. et al. J. Am. Chem. Soc. 2009, 131, 10822.
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Claisen Rearrangement
• Metal/Base Catalyzed Isomerization + Claisen
– Alkyne Addition/Cycloisomerization
Ovaska, T. V. et al. Org. Lett. 2008, 10, 3287.
Yamamoto, Y. et al. Chem. Lett. 2005, 34, 174.
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Claisen Rearrangement
• Charge Accelerated Claisen Rearrangement
– Bellus-Claisen Rearrangement: An Iterative Version
MacMillan, D. W. C. et al. J. Am. Chem. Soc. 2001, 123, 2448.
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Claisen Rearrangement
• Charge Accelerated Claisen Rearrangement
– Metal-Catalyzed Oxonium/Sulfonium Claisen Rearrangement
Rainier, J. D. et al. Angew. Chem. 2008, 120, 5454.; Angew. Chem. Int. Ed. 2008, 47, 5374.
Rhee, Y. H. et al. Angew. Chem. 2008, 120, 2295.; Angew. Chem. Int. Ed. 2008, 47, 2263.
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Content
• Introduction
• Cope Rearrangement
• Claisen Rearrangement
• Cationic Hetero-Cope Rearrangement
• Summary
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Cationic Hetero-Cope
• Aza-Cope Rearrangement
Rueping, M. et al. Angew. Chem. 2008, 120, 10244.; Angew. Chem. Int. Ed. 2008, 47, 10090.
Overman, L. E. et al. J. Am. Chem. Soc. 2010, 132, 3272.
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Cationic Hetero-Cope
• Aza-Cope Rearrangement
– Aza-Cope/Mannich Cascade: Overman’s Strategy
L. E. Overman, et al. J. Am. Chem. Soc. 2010, 132, 4894.
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Cationic Hetero-Cope
• Oxonia-Cope Rearrangement
Nokami, J. et al. J. Am. Chem. Soc. 2000, 122, 1310.
Rychnovsky, S. D. et al. J. Am. Chem. Soc. 2005, 127, 16044.
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Content
• Introduction
• Cope Rearrangement
• Claisen Rearrangement
• Cationic Hetero-Cope Rearrangement
• Summary
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Summary
Highly Predictable
Reaction Path
Well Defined
Stereochemistry
Efficiency
Complexity
Catalyst Activity
Deep Mechanistic
Understanding &
Delicate Design
Diversity
Selectivity
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Summary
• Reviews on Related Topic
Jones, A. C. & Stoltz, B. M. et al. Angew. Chem. Int. Ed. 2014, 53, 2556 and reviews therein.
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Acknowledgement
•
Prof. Luo, Prof. Yang, Prof. Chen, Prof. Tang
•
Ms. Yu Xuerong, Mr. Yuan Haosen
•
All Members in Luo Lab and Yang Lab
•
All Former Members in Yang Lab (2010-2013)
•
Everyone Here
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Thank You!
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