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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. https://resolver.caltech.edu/CaltechAUTHORS:20170411-135947566

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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.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1021/ja017641uDOIArticle
http://pubs.acs.org/doi/full/10.1021/ja017641uPublisherArticle
http://pubs.acs.org/doi/suppl/10.1021/ja017641uPublisherSupporting Information
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.
Funders:
Funding AgencyGrant Number
AstraZenecaUNSPECIFIED
Boehringer-IngelheimUNSPECIFIED
DupontUNSPECIFIED
GlaxoSmithKlineUNSPECIFIED
Johnson and JohnsonUNSPECIFIED
MateriaUNSPECIFIED
Merck Research LaboratoriesUNSPECIFIED
PfizerUNSPECIFIED
PharmaciaUNSPECIFIED
Roche BiosciencesUNSPECIFIED
NSF Predoctoral FellowshipUNSPECIFIED
Cottrell Scholar of Research CorporationUNSPECIFIED
Issue or Number:11
Record Number:CaltechAUTHORS:20170411-135947566
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20170411-135947566
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
Collection:CaltechAUTHORS
Deposited By: Ruth Sustaita
Deposited On:11 Apr 2017 21:41
Last Modified:03 Oct 2019 17:02

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