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The First General Enantioselective Catalytic Diels−Alder Reaction with Simple α,β-Unsaturated Ketones

Northrup, Alan B. and MacMillan, David W. C. (2002) The First General Enantioselective Catalytic Diels−Alder Reaction with Simple α,β-Unsaturated Ketones. Journal of the American Chemical Society, 124 (11). pp. 2458-2460. ISSN 0002-7863. doi:10.1021/ja017641u.

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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.

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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.
Funding AgencyGrant Number
Johnson and JohnsonUNSPECIFIED
Merck Research LaboratoriesUNSPECIFIED
Roche BiosciencesUNSPECIFIED
NSF Predoctoral FellowshipUNSPECIFIED
Cottrell Scholar of Research CorporationUNSPECIFIED
Issue or Number:11
Record Number:CaltechAUTHORS:20170411-135947566
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Official Citation:The First General Enantioselective Catalytic Diels−Alder Reaction with Simple α,β-Unsaturated Ketones Alan B. Northrup and David W. C. MacMillan Journal of the American Chemical Society 2002 124 (11), 2458-2460 DOI: 10.1021/ja017641u
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:76519
Deposited By: Ruth Sustaita
Deposited On:11 Apr 2017 21:41
Last Modified:15 Nov 2021 17:00

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