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Phosphoramidite Gold(I)-Catalyzed Diastereo- and Enantioselective Synthesis of 3,4-Substituted Pyrrolidines

González, Ana Z. and Benitez, Diego and Tkatchouk, Ekaterina and Goddard, William A., III and Toste, F. Dean (2011) Phosphoramidite Gold(I)-Catalyzed Diastereo- and Enantioselective Synthesis of 3,4-Substituted Pyrrolidines. Journal of the American Chemical Society, 133 (14). pp. 5500-5507. ISSN 0002-7863. PMCID PMC3071892. https://resolver.caltech.edu/CaltechAUTHORS:20110519-102426786

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Abstract

In this article the utility of phosphoramidite ligands in enantioselective AuI catalysis was explored in the development of highly diastereo- and enantioselective AuI-catalyzed cycloadditions of allenenes. A Au^I-catalyzed synthesis of 3,4-disubstituted pyrrolidines and γ-lactams is described. This reaction proceeds through the enantioselective AuI-catalyzed cyclization of allenenes to form a carbocationic intermediate that is trapped by an exogenous nucleophile, resulting in the highly diastereoselective construction of three contiguous stereogenic centers. A computational study (DFT) was also performed to gain some insight into the underlying mechanisms of these cycloadditions. The utility of this new methodology was demonstrated through the formal synthesis of (−)-isocynometrine.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1021/ja200084aDOIArticle
http://pubs.acs.org/doi/full/10.1021/ja200084aPublisherArticle
https://www.ncbi.nlm.nih.gov/pmc/articles/PMC3071892PubMed CentralArticle
ORCID:
AuthorORCID
Goddard, William A., III0000-0003-0097-5716
Toste, F. Dean0000-0001-8018-2198
Additional Information:© 2011 American Chemical Society. Received January 4, 2011. Published March 23, 2011. We gratefully acknowledge funding from the National Institute of General Medical Services (GM073932) and Amgen. A.Z. G. thanks the NIH for a postdoctoral fellowship. We thank Vincent Medrán and Pablo Mauleόn for preliminary experiments and Johnson Matthey for a gift of AuCl_3. We would also like to thank Dr. Antonio DiPasquale for his assistance in collecting and analyzing crystallographic data. Computational resources were partially funded as part of the Center for Catalytic Hydrocarbon Functionalization, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under Award Number DE-SC0001298.
Funders:
Funding AgencyGrant Number
NIHGM073932
AmgenUNSPECIFIED
Department of Energy (DOE)DE-SC0001298
NIH Postdoctoral FellowshipUNSPECIFIED
Issue or Number:14
PubMed Central ID:PMC3071892
Record Number:CaltechAUTHORS:20110519-102426786
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20110519-102426786
Official Citation:Phosphoramidite Gold(I)-Catalyzed Diastereo- and Enantioselective Synthesis of 3,4-Substituted Pyrrolidines Ana Z. Gonzlez, Diego Benitez, Ekaterina Tkatchouk, William A. Goddard III, F. Dean Toste Journal of the American Chemical Society 2011 133 (14), 5500-5507
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:23729
Collection:CaltechAUTHORS
Deposited By: Ruth Sustaita
Deposited On:19 May 2011 20:26
Last Modified:28 Oct 2019 18:17

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