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Total Syntheses of the C₁₉ Diterpenoid Alkaloids (–)-Talatisamine, (–)-Liljestrandisine, and (–)-Liljestrandinine by a Fragment Coupling Approach

Wong, Alice R. and Fastuca, Nicholas J. and Mak, Victor W. and Kerkovius, Jeffrey K. and Stevenson, Susan M. and Reisman, Sarah E. (2021) Total Syntheses of the C₁₉ Diterpenoid Alkaloids (–)-Talatisamine, (–)-Liljestrandisine, and (–)-Liljestrandinine by a Fragment Coupling Approach. ACS Central Science, 7 (8). pp. 1311-1316. ISSN 2374-7951. PMCID PMC8393236. doi:10.1021/acscentsci.1c00540. https://resolver.caltech.edu/CaltechAUTHORS:20210513-103036703

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Abstract

The C19 diterpenoid alkaloids (C19 DTAs) are a large family of natural products, many of which modulate the activity of ion channels in vivo and are therefore of interest for the study of neurological and cardiovascular diseases. The complex architectures of these molecules continue to challenge the state-of-the art in chemical synthesis, particularly with respect to efficient assembly of their polcyclic ring systems. Here, we report the total syntheses of (−)-talatisamine, (−)-liljestrandisine, and (−)-liljestrandinine, three aconitine-type C19 DTAs, using a fragment coupling strategy. Key to this approach is a 1,2-addition/semipinacol rearrangement sequence which efficiently joins two complex fragments and sets an all-carbon quaternary center.


Item Type:Article
Related URLs:
URLURL TypeDescription
https://doi.org/10.1021/acscentsci.1c00540DOIArticle
https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8393236PubMed CentralArticle
https://doi.org/10.26434/chemrxiv.14517063.v2DOIDiscussion Paper - version 2
https://doi.org/10.26434/chemrxiv.14517063.v1DOIDiscussion Paper - version 1
ORCID:
AuthorORCID
Wong, Alice R.0000-0002-1038-4453
Fastuca, Nicholas J.0000-0003-4081-6031
Kerkovius, Jeffrey K.0000-0001-5692-0285
Stevenson, Susan M.0000-0002-9627-0464
Reisman, Sarah E.0000-0001-8244-9300
Alternate Title:Total Syntheses of the C19 Diterpenoid Alkaloids (–)-Talatisamine, (–)-Liljestrandisine, and (–)-Liljestrandinine by a Fragment Coupling Approach
Additional Information:© 2021 The Authors. Published by American Chemical Society. Attribution-NonCommercial-NoDerivatives 4.0 International (CC BY-NC-ND 4.0). Received: May 5, 2021; Published: July 27, 2021. Dr. Scott Virgil and the Caltech Center for Catalysis and Chemical Synthesis are gratefully acknowledged for access to analytical equipment. Fellowship support was provided by the NSF (V.W.M., A.R.W., Grant No. DGE-1144469), Natural Sciences and Engineering Research Council of Canada (J.K.K., Grant No. 532535), and the NIH (F32 GM122386 to S.M.S. and T32 GM07616 to N.J.F.). S.E.R. is a Heritage Medical Research Institute Investigator and acknowledges financial support from the NIH (R35GM118191). The authors declare no competing financial interest.
Group:Heritage Medical Research Institute
Funders:
Funding AgencyGrant Number
NSF Graduate Research FellowshipDGE-1144469
Natural Sciences and Engineering Research Council of Canada (NSERC)532535
NIH Postdoctoral FellowshipF32 GM122386
NIH Predoctoral FellowshipT32 GM07616
Heritage Medical Research InstituteUNSPECIFIED
NIHR35GM118191
Subject Keywords:Redox reactions, Alcohols, Anions, Rearrangement, Ketones
Issue or Number:8
PubMed Central ID:PMC8393236
DOI:10.1021/acscentsci.1c00540
Record Number:CaltechAUTHORS:20210513-103036703
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20210513-103036703
Official Citation:Total Syntheses of the C19 Diterpenoid Alkaloids (−)-Talatisamine, (−)-Liljestrandisine, and (−)-Liljestrandinine by a Fragment Coupling Approach. Alice R. Wong, Nicholas J. Fastuca, Victor W. Mak, Jeffrey K. Kerkovius, Susan M. Stevenson, and Sarah E. Reisman. ACS Central Science 2021 7 (8), 1311-1316; DOI: 10.1021/acscentsci.1c00540
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:109113
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:13 May 2021 17:49
Last Modified:02 Sep 2021 16:03

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