Site-Selective Functionalization of Unactivated Allylic C–H Bonds via Direct Deprotonation with KTMP: Application to the Formal Total Synthesis of (+)-Artemisinin from Amorphadiene

[Image: see text] The site-selective functionalization of unactivated allylic C–H bonds via direct deprotonation using KTMP is described. The conversion of amorphadiene to artemisinic alcohol via a simple, highly regioselective deprotonation over 4 other possible allylic sites is shown with further...

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Autores principales: Clanton, Nicholas A., Wilson, Nicolas A., Ortiz, Eliezer, Blumberg, Shawn T., Frantz, Doug E.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2023
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9841608/
https://www.ncbi.nlm.nih.gov/pubmed/36592432
http://dx.doi.org/10.1021/acs.orglett.2c04145
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author Clanton, Nicholas A.
Wilson, Nicolas A.
Ortiz, Eliezer
Blumberg, Shawn T.
Frantz, Doug E.
author_facet Clanton, Nicholas A.
Wilson, Nicolas A.
Ortiz, Eliezer
Blumberg, Shawn T.
Frantz, Doug E.
author_sort Clanton, Nicholas A.
collection PubMed
description [Image: see text] The site-selective functionalization of unactivated allylic C–H bonds via direct deprotonation using KTMP is described. The conversion of amorphadiene to artemisinic alcohol via a simple, highly regioselective deprotonation over 4 other possible allylic sites is shown with further extrapolation to the first large-scale telescoped chemical synthesis of artemisinic acid from amorphadiene. Finally, application of the method for the successful site-selective functionalization of unactivated allylic C–H bonds in other terpene-based natural products is also highlighted.
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spelling pubmed-98416082023-01-17 Site-Selective Functionalization of Unactivated Allylic C–H Bonds via Direct Deprotonation with KTMP: Application to the Formal Total Synthesis of (+)-Artemisinin from Amorphadiene Clanton, Nicholas A. Wilson, Nicolas A. Ortiz, Eliezer Blumberg, Shawn T. Frantz, Doug E. Org Lett [Image: see text] The site-selective functionalization of unactivated allylic C–H bonds via direct deprotonation using KTMP is described. The conversion of amorphadiene to artemisinic alcohol via a simple, highly regioselective deprotonation over 4 other possible allylic sites is shown with further extrapolation to the first large-scale telescoped chemical synthesis of artemisinic acid from amorphadiene. Finally, application of the method for the successful site-selective functionalization of unactivated allylic C–H bonds in other terpene-based natural products is also highlighted. American Chemical Society 2023-01-02 /pmc/articles/PMC9841608/ /pubmed/36592432 http://dx.doi.org/10.1021/acs.orglett.2c04145 Text en © 2023 The Authors. Published by American Chemical Society https://creativecommons.org/licenses/by/4.0/Permits the broadest form of re-use including for commercial purposes, provided that author attribution and integrity are maintained (https://creativecommons.org/licenses/by/4.0/).
spellingShingle Clanton, Nicholas A.
Wilson, Nicolas A.
Ortiz, Eliezer
Blumberg, Shawn T.
Frantz, Doug E.
Site-Selective Functionalization of Unactivated Allylic C–H Bonds via Direct Deprotonation with KTMP: Application to the Formal Total Synthesis of (+)-Artemisinin from Amorphadiene
title Site-Selective Functionalization of Unactivated Allylic C–H Bonds via Direct Deprotonation with KTMP: Application to the Formal Total Synthesis of (+)-Artemisinin from Amorphadiene
title_full Site-Selective Functionalization of Unactivated Allylic C–H Bonds via Direct Deprotonation with KTMP: Application to the Formal Total Synthesis of (+)-Artemisinin from Amorphadiene
title_fullStr Site-Selective Functionalization of Unactivated Allylic C–H Bonds via Direct Deprotonation with KTMP: Application to the Formal Total Synthesis of (+)-Artemisinin from Amorphadiene
title_full_unstemmed Site-Selective Functionalization of Unactivated Allylic C–H Bonds via Direct Deprotonation with KTMP: Application to the Formal Total Synthesis of (+)-Artemisinin from Amorphadiene
title_short Site-Selective Functionalization of Unactivated Allylic C–H Bonds via Direct Deprotonation with KTMP: Application to the Formal Total Synthesis of (+)-Artemisinin from Amorphadiene
title_sort site-selective functionalization of unactivated allylic c–h bonds via direct deprotonation with ktmp: application to the formal total synthesis of (+)-artemisinin from amorphadiene
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9841608/
https://www.ncbi.nlm.nih.gov/pubmed/36592432
http://dx.doi.org/10.1021/acs.orglett.2c04145
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