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Development of a New Lewis Acid-Catalyzed [3,3]-Sigmatropic Rearrangement: The Allenoate-Claisen Rearrangement

Lambert, Tristan H. and MacMillan, David W. C. (2002) Development of a New Lewis Acid-Catalyzed [3,3]-Sigmatropic Rearrangement: The Allenoate-Claisen Rearrangement. Journal of the American Chemical Society, 124 (46). pp. 13646-13647. ISSN 0002-7863. https://resolver.caltech.edu/CaltechAUTHORS:20170321-110525126

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Abstract

A new Lewis acid-catalyzed Claisen rearrangement has been developed that allows the stereoselective construction of β-amino-α,β,ε,ζ-unsaturated-γ,δ-disubstituted esters from simple allylic amines and allenoate esters. This reaction, which is contingent upon the use of Lewis acid, can be conducted with a range of metal salts (Yb(OTf)_3, AlCl_3, Sn(OTf)_2, Cu(OTf)_2, MgBr_2·Et_2O, FeCl_3, Zn(OTf)2) with catalyst loadings as low as 5 mol %. This catalytic process provides access to a diverse range of β-amino-α,β,ε,ζ-unsaturated-γ,δ-disubstituted esters in high yield and with excellent levels of diastereoselectivity for a series of allyl pyrrolidines (R_1 = H, Me, i-Pr, Ph, NR_2 = pyrrolidine, piperidine, Nme_2; ≥81% yield, ≥94:6 syn:anti) and allenoate esters (R_2 = H, Me, i-Pr, Ph, allyl, NPht, Cl; ≥75% yield, ≥91:9 syn:anti). The capacity of this new Claisen rearrangement to provide catalytic access to elusive structural motifs has also been demonstrated in the stereospecific formation of quaternary carbon bearing frameworks arising from geranyl- and neryl pyrrolidine (≥93% yield, >98:2 dr).


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http://dx.doi.org/10.1021/ja028090qDOIArticle
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http://pubs.acs.org/doi/suppl/10.1021/ja028090qPublisherSupporting Information
Additional Information:© 2002 American Chemical Society. Received August 9, 2002. Publication Date (Web): October 29, 2002. Support was provided by the NIHGMS (R01 GM61214-01) and the UC-AIDS Research Program. We are grateful to Dr. T. P. Yoon (Harvard University) for helpful discussions.
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NIHR01 GM61214-01
University of California AIDS Research ProgramUNSPECIFIED
Issue or Number:46
Record Number:CaltechAUTHORS:20170321-110525126
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20170321-110525126
Official Citation:Development of a New Lewis Acid-Catalyzed [3,3]-Sigmatropic Rearrangement:  The Allenoate-Claisen Rearrangement Tristan H. Lambert and David W. C. MacMillan Journal of the American Chemical Society 2002 124 (46), 13646-13647 DOI: 10.1021/ja028090q
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:75272
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:21 Mar 2017 19:22
Last Modified:03 Oct 2019 16:48

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