Asymmetric Synthesis of β-Substituted α-Methylenebutyro- lactones via TRIP-Catalyzed Allylation: Mechanistic Studies and Application to the Synthesis of (S)-(−)-Hydroxymatairesinol

Asymmetric allylation of (hetero)aromatic aldehydes by a zinc(II)-allylbutyrolactone species catalyzed by a chiral BINOL-type phosphoric acid gave β-substituted α-methylenebutyrolactones in 68 to >99% ee and 52–91% isolated yield. DFT studies on the intermediate Zn(2+)-complex – crucial for chira...

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Autores principales: Fuchs, Michael, Schober, Markus, Orthaber, Andreas, Faber, Kurt
Formato: Online Artículo Texto
Lenguaje:English
Publicado: WILEY-VCH Verlag 2013
Materias:
Communications
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC3883096/
https://www.ncbi.nlm.nih.gov/pubmed/24415960
http://dx.doi.org/10.1002/adsc.201300392
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author Fuchs, Michael
Schober, Markus
Orthaber, Andreas
Faber, Kurt
author_facet Fuchs, Michael
Schober, Markus
Orthaber, Andreas
Faber, Kurt
author_sort Fuchs, Michael
collection PubMed
description Asymmetric allylation of (hetero)aromatic aldehydes by a zinc(II)-allylbutyrolactone species catalyzed by a chiral BINOL-type phosphoric acid gave β-substituted α-methylenebutyrolactones in 68 to >99% ee and 52–91% isolated yield. DFT studies on the intermediate Zn(2+)-complex – crucial for chiral induction – suggest a six-membered ring intermediate, which allows the phosphoric acid moiety to activate the aldehyde. The methodology was applied to the synthesis of the antitumour natural product (S)-(−)-hydroxymatairesinol.
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spelling pubmed-38830962014-01-10 Asymmetric Synthesis of β-Substituted α-Methylenebutyro- lactones via TRIP-Catalyzed Allylation: Mechanistic Studies and Application to the Synthesis of (S)-(−)-Hydroxymatairesinol Fuchs, Michael Schober, Markus Orthaber, Andreas Faber, Kurt Adv Synth Catal Communications Asymmetric allylation of (hetero)aromatic aldehydes by a zinc(II)-allylbutyrolactone species catalyzed by a chiral BINOL-type phosphoric acid gave β-substituted α-methylenebutyrolactones in 68 to >99% ee and 52–91% isolated yield. DFT studies on the intermediate Zn(2+)-complex – crucial for chiral induction – suggest a six-membered ring intermediate, which allows the phosphoric acid moiety to activate the aldehyde. The methodology was applied to the synthesis of the antitumour natural product (S)-(−)-hydroxymatairesinol. WILEY-VCH Verlag 2013-09-16 2013-08-29 /pmc/articles/PMC3883096/ /pubmed/24415960 http://dx.doi.org/10.1002/adsc.201300392 Text en © 2013 The Authors. Published by Wiley-VCH Verlag GmbH &Co. KGaA. This is an open access article under the terms of the Creative Commons Attribution-NonCommercial License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited and is not used for commercial purposes. http://creativecommons.org/licenses/by/2.5/ Re-use of this article is permitted in accordance with the Creative Commons Deed, Attribution 2.5, which does not permit commercial exploitation.
spellingShingle Communications
Fuchs, Michael
Schober, Markus
Orthaber, Andreas
Faber, Kurt
Asymmetric Synthesis of β-Substituted α-Methylenebutyro- lactones via TRIP-Catalyzed Allylation: Mechanistic Studies and Application to the Synthesis of (S)-(−)-Hydroxymatairesinol
title Asymmetric Synthesis of β-Substituted α-Methylenebutyro- lactones via TRIP-Catalyzed Allylation: Mechanistic Studies and Application to the Synthesis of (S)-(−)-Hydroxymatairesinol
title_full Asymmetric Synthesis of β-Substituted α-Methylenebutyro- lactones via TRIP-Catalyzed Allylation: Mechanistic Studies and Application to the Synthesis of (S)-(−)-Hydroxymatairesinol
title_fullStr Asymmetric Synthesis of β-Substituted α-Methylenebutyro- lactones via TRIP-Catalyzed Allylation: Mechanistic Studies and Application to the Synthesis of (S)-(−)-Hydroxymatairesinol
title_full_unstemmed Asymmetric Synthesis of β-Substituted α-Methylenebutyro- lactones via TRIP-Catalyzed Allylation: Mechanistic Studies and Application to the Synthesis of (S)-(−)-Hydroxymatairesinol
title_short Asymmetric Synthesis of β-Substituted α-Methylenebutyro- lactones via TRIP-Catalyzed Allylation: Mechanistic Studies and Application to the Synthesis of (S)-(−)-Hydroxymatairesinol
title_sort asymmetric synthesis of β-substituted α-methylenebutyro- lactones via trip-catalyzed allylation: mechanistic studies and application to the synthesis of (s)-(−)-hydroxymatairesinol
topic Communications
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC3883096/
https://www.ncbi.nlm.nih.gov/pubmed/24415960
http://dx.doi.org/10.1002/adsc.201300392
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