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Enantioselective Pd-Catalyzed Allylic Alkylation Reactions of Dihydropyrido[1,2-a]indolone Substrates: Efficient Syntheses of (−)-Goniomitine, (+)-Aspidospermidine, and (−)-Quebrachamine

Pritchett, Beau P. and Kikuchi, Jun and Numajiri, Yoshitaka and Stoltz, Brian M. (2016) Enantioselective Pd-Catalyzed Allylic Alkylation Reactions of Dihydropyrido[1,2-a]indolone Substrates: Efficient Syntheses of (−)-Goniomitine, (+)-Aspidospermidine, and (−)-Quebrachamine. Angewandte Chemie International Edition, 55 (43). pp. 13529-13532. ISSN 1433-7851. PMCID PMC5207349. doi:10.1002/anie.201608138. https://resolver.caltech.edu/CaltechAUTHORS:20160927-100108036

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Abstract

The successful application of dihydropyrido[1,2-a]indolone (DHPI) substrates in Pd-catalyzed asymmetric allylic alkylation chemistry facilitates rapid access to multiple alkaloid frameworks in an enantioselective fashion. Strategic bromination at the indole C3 position greatly improved the allylic alkylation chemistry and enabled a highly efficient Negishi cross-coupling downstream. The first catalytic enantioselective total synthesis of (−)-goniomitine, along with divergent formal syntheses of (+)-aspidospermidine and (−)-quebrachamine, are reported herein.


Item Type:Article
Related URLs:
URLURL TypeDescription
https://doi.org/10.1002/anie.201608138DOIArticle
https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5207349PubMed CentralArticle
ORCID:
AuthorORCID
Pritchett, Beau P.0000-0001-9922-9160
Kikuchi, Jun0000-0001-9892-8832
Stoltz, Brian M.0000-0001-9837-1528
Additional Information:© 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim. Received: August 19, 2016; Revised: September 7, 2016; First published: 26 September 2016. The authors wish to thank NIH-NIGMS (R01GM080269), Amgen, the Gordon and Betty Moore Foundation, and Caltech for financial support. B.P.P. thanks the NSF for a predoctoral fellowship (Grant DGE-1144469). Y.N. thanks Toray Industries Inc. for a postdoctoral fellowship. The authors thank Mona Shahgholi and Naseem Torian for mass spectrometry assistance, and Dr. Scott Virgil (Caltech) and the Caltech Center for Catalysis and Chemical Synthesis, for instrumentation assistance.
Funders:
Funding AgencyGrant Number
NIHR01GM080269-01
AmgenUNSPECIFIED
Gordon and Betty Moore FoundationUNSPECIFIED
CaltechUNSPECIFIED
NSF Graduate Research FellowshipDGE-1144469
Toray Industries Inc.UNSPECIFIED
Subject Keywords:alkaloids; allylic alkylation; asymmetric catalysis; quaternary centers; total synthesis
Issue or Number:43
PubMed Central ID:PMC5207349
DOI:10.1002/anie.201608138
Record Number:CaltechAUTHORS:20160927-100108036
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20160927-100108036
Official Citation:B. P. Pritchett, J. Kikuchi, Y. Numajiri, B. M. Stoltz, Angew. Chem. Int. Ed. 2016, 55, 13529
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:70603
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:28 Sep 2016 17:22
Last Modified:14 Apr 2022 17:44

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