The First General Enantioselective Catalytic Diels−Alder Reaction with Simple α,β-Unsaturated Ketones
- Creators
- Northrup, Alan B.
- MacMillan, David W. C.
Abstract
The first general approach to enantioselective catalysis of the Diels−Alder reaction with simple ketone dienophiles has been accomplished. The use of iminium catalysis has enabled enantioselective access to a fundamental Diels−Alder reaction variant that has previously been unavailable using chiral Lewis acid catalysis. A new chiral amine catalyst has been developed that allows a variety of monodentate cyclic and acyclic ketones to successfully participate in enantioselective [4 + 2] cycloadditions. A wide spectrum of cyclic and acyclic diene substrates can also be accommodated in this new organocatalytic transformation. A computational model is provided that is in accord with the sense of enantioinduction observed for all reactions conducted during the course of this study.
Additional Information
© 2002 American Chemical Society. Received 29 November 2001. Published online 23 February 2002. Published in print 1 March 2002. Financial support was provided by kind gifts from AstraZeneca, Boehringer-Ingelheim, Dupont, GlaxoSmithKline, Johnson and Johnson, Lilly, Materia, Merck Research Laboratories, Pfizer, Pharmacia, and Roche Biosciences. We also thank Great Lakes for their generous donation of (S)-phenylalanine. D.W.C.M is grateful for support from Research Corporation under the Cottrell Scholarship program. A.B.N. is grateful for a NSF predoctoral fellowship. Note Added in Proof. Shortly prior to publication it came to the authors attention that an enantioselective boron-catalyzed ketone Diels−Alder reaction has been accomplished. This work will be submitted for communication in the near future. Joel M. Hawkins, Pfizer Global Research, personal communication.Attached Files
Supplemental Material - ja017641u_s1.pdf
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Additional details
- Eprint ID
- 76519
- Resolver ID
- CaltechAUTHORS:20170411-135947566
- AstraZeneca
- Boehringer-Ingelheim
- Dupont
- GlaxoSmithKline
- Johnson and Johnson
- Materia
- Merck Research Laboratories
- Pfizer
- Pharmacia
- Roche Biosciences
- NSF Predoctoral Fellowship
- Cottrell Scholar of Research Corporation
- Created
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2017-04-11Created from EPrint's datestamp field
- Updated
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2021-11-15Created from EPrint's last_modified field