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Catalytic enantioselective synthesis of carbocyclic and heterocyclic spiranes via a decarboxylative aldol cyclization

Inanaga, Kazato and Wollenburg, Marco and Bachman, Shoshana and Hafeman, Nicholas J. and Stoltz, Brian M. (2020) Catalytic enantioselective synthesis of carbocyclic and heterocyclic spiranes via a decarboxylative aldol cyclization. Chemical Science, 11 (28). pp. 7390-7395. ISSN 2041-6520. PMCID PMC7574022. https://resolver.caltech.edu/CaltechAUTHORS:20200702-103837298

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Abstract

The synthesis of a variety of enantioenriched 1,3-diketospiranes from the corresponding racemic allyl β-ketoesters via an interrupted asymmetric allylic alkylation is disclosed. Substrates possessing pendant aldehydes undergo decarboxylative enolate formation in the presence of a chiral Pd catalyst and subsequently participate in an enantio- and diastereoselective, intramolecular aldol reaction to furnish spirocyclic β-hydroxy ketones which may be oxidized to the corresponding enantioenriched diketospiranes. Additionally, this chemistry has been extended to α-allylcarboxy lactam substrates leading to a formal synthesis of the natural product (−)-isonitramine.


Item Type:Article
Related URLs:
URLURL TypeDescription
https://doi.org/10.1039/d0sc02366cDOIArticle
http://www.ncbi.nlm.nih.gov/pmc/articles/pmc7574022/PubMed CentralArticle
ORCID:
AuthorORCID
Hafeman, Nicholas J.0000-0001-7525-7597
Stoltz, Brian M.0000-0001-9837-1528
Additional Information:© 2020 The Royal Society of Chemistry. This article is licensed under a Creative Commons Attribution-NonCommercial 3.0 Unported Licence. All publication charges for this article have been paid for by the Royal Society of Chemistry. Received 26th April 2020; Accepted 20th June 2020; First published 23 Jun 2020. This manuscript is dedicated to the memory of Prof. Teruaki Mukaiyama. The authors wish to thank NIH-NIGMS (R01GM080269), Astellas Pharma, Inc. (postdoctoral fellowship to K. I.), the Alfried Krupp von Bohlen and Halbach Foundation (fellowship to M. W.) and Amgen, Inc. (graduate fellowship to S. B.). We also thank Dr Scott C. Virgil for his support with chromatographic analysis, high-resolution mass analysis, and assistance during the crystallization process. The authors declare no conflicts of interest.
Funders:
Funding AgencyGrant Number
NIHR01GM080269
Astellas Pharma, Inc.UNSPECIFIED
Alfried Krupp von Bohlen and Halbach FoundationUNSPECIFIED
AmgenUNSPECIFIED
Royal Society of ChemistryUNSPECIFIED
Issue or Number:28
PubMed Central ID:PMC7574022
Record Number:CaltechAUTHORS:20200702-103837298
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20200702-103837298
Official Citation:Catalytic enantioselective synthesis of carbocyclic and heterocyclic spiranes via a decarboxylative aldol cyclization. Chem. Sci., 2020, 11, 7390-7395; doi: 10.1039/d0sc02366c
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:104205
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:02 Jul 2020 17:46
Last Modified:04 Nov 2020 17:00

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