The Type II Intramolecular Diels-Alder Reaction: …gbdong.cm.utexas.edu/seminar/old/The Type...
Transcript of The Type II Intramolecular Diels-Alder Reaction: …gbdong.cm.utexas.edu/seminar/old/The Type...
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The Type II Intramolecular Diels-Alder Reaction:
Synthesis and Chemistry of Bridgehead Alkenes
2013. 10. 24
Haye Min Ko
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Kenneth J. Shea was born in Queens, New York. He received his B.S. and M.S.degrees in Chemistry from the University of Toledo. He did his graduatestudies in physical organic chemistry at Pennsylvania State University.Following postdoctoral studies at the California Institute of Technology, hejoined the faculty of the University of California at Irvine in 1974. His researchinterests are in synthetic and mechanistic organic chemistry and polymer andmaterials chemistry.
Kenneth J. Shea
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Bredt’s Rule vs Bridged alkene
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Introduction: Intramolecular Diels-Alder
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Type II Intramolecular Diels-Alder
> 300 oCAccidental discovery during a mechanistic study
of the Cope rearrangement.Shea, K. J., J. Am. Chem. Soc., 1978, 100, 6519
Shea, K. J., Angew. Chem. Int. Ed., 2001, 40, 820
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Development of the Scope of the Reaction
Shea, K. J., J. Am. Chem. Soc., 1982, 104, 5708Shea, K. J., J. Am. Chem. Soc., 1985, 107, 4791
Activated Dienophiles Lewis Acid Catalyst
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Shea, K. J., Tetrahedron Lett., 1990, 31, 6843Kanematsu, K., Tetrahedron Lett., 1986, 27, 4205
Acetylenic and Allenic Dienophiles
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Chou, T. S., Chen, H. C., Tetrahedron Lett., 1996, 37, 7823Chou, T. S., Chen, H. C., Tetrahedron Lett., 1999, 40, 961
Masked Dienes and Dienophiles
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Shea, K. J., J. Am. Chem. Soc., 1990, 112, 8627Shea, K. J., J. Am. Chem. Soc., 1993, 115, 2248
Shea, K. J., Org. Lett., 2000, 2, 1473
Hetero Diels-Alder Reactions
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Jung, M. E., Tetrahedron Lett., 1976, 2935Shea, K. J., J. Am. Chem. Soc., 1987, 109, 447
Regio- and Stereochemical Control
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Disposable Tethers between Diene and Dienophile
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Enantioselective Intramolecular Diels-Alder
Macmillan, David W. C., J. Am. Chem. Soc., 2005, 127, 11616Nicolaou, K. C., Angew. Chem. Int. Ed., 2000, 39, 1829
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Stereoselective Elaboration
Addition to the Bridged Double Bond
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Functionalization of the Bridged Ring System
Shea, K. J., J. Org. Chem., 1996, 61, 7438Shea, K. J., Tetrahedron Lett., 1992, 33, 4261
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Bridged to Fused Ring Interchange
Shea, K. J., Tetrahedron Lett., 1995, 36, 7177Tetrahedron Lett., 1996, 37, 949
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Ring Expansion of Bridged Alkenes
exo addition of dichlorocarbene
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Applications in Natual Product Synthesis
Taxanes
Shea, K. J., Angew. Chem. Int. Ed., 1983, 22, 419
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Taxanes (Yadav)
Type II IMDA & Wittig rearrangement
Yadav, J. S., Tetrahedron Lett., 1991, 32, 2629
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Taxanes (Phillips and Abell)
Phillips, A. J., Morris, J. C., Abell, A. D., Tetrahedron Lett., 2000, 41, 2723
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Taxanes
Shea, K. J., Tetrahedron Lett., 1994, 35, 1317
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Taxanes
Winkler, J. D., Tetrahedron Lett., 1995, 36, 687
J. Org. Chem., 1997, 62, 2957
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Applications in Natual Product Synthesis
Esperamicin
Shea, K. J., Angew. Chem. Int. Ed., 1983, 22, 419
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Applications in Natual Product Synthesis
Total Synthesis of (+)-Adrenosterone
Shea, K. J., J. Am. Chem. Soc., 1996, 118, 4711
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Total Syntheses of Plocamium monoterpene, ledol and ledene
Shea, K. J., J. Org. Chem., 1996, 61, 7438J. Org. Chem., 1997, 62, 8962
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Total Synthesis of CP-264,114 (racemic)
Nicolaou, K. C., Angew. Chem. Int. Ed., 1999, 38, 1676Angew. Chem. Int. Ed., 2000, 39, 1829
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Total Synthesis of CP-264,114 (asymmetric)
Nicolaou, K. C., Angew. Chem. Int. Ed., 1999, 38, 1676Angew. Chem. Int. Ed., 2000, 39, 1829
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• Type II intramolecular Diels-Alder reaction
- provideds bridgedhead alkenes
- access to other compounds through disposable tethers, bridged to fused interchange,
and ring expansion
- the most useful synthetic method for forming 7, 8-membered rings embeded in the
bicyclic structure
- used in natural product synthesis
Conclusion
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Thank you
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Quiz !
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Quiz !