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Short Enantioselective Total Synthesis of Tatanan A and 3‐epi‐Tatanan A Using Assembly‐Line Synthesis

Short and highly stereoselective total syntheses of the sesquilignan natural product tatanan A and its C3 epimer are described. An assembly‐line synthesis approach, using iterative lithiation–borylation reactions, was applied to install the three contiguous stereocenters with high enantio‐ and diast...

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Detalles Bibliográficos
Autores principales: Noble, Adam, Roesner, Stefan, Aggarwal, Varinder K.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: John Wiley and Sons Inc. 2016
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5215435/
https://www.ncbi.nlm.nih.gov/pubmed/27865037
http://dx.doi.org/10.1002/anie.201609598
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author Noble, Adam
Roesner, Stefan
Aggarwal, Varinder K.
author_facet Noble, Adam
Roesner, Stefan
Aggarwal, Varinder K.
author_sort Noble, Adam
collection PubMed
description Short and highly stereoselective total syntheses of the sesquilignan natural product tatanan A and its C3 epimer are described. An assembly‐line synthesis approach, using iterative lithiation–borylation reactions, was applied to install the three contiguous stereocenters with high enantio‐ and diastereoselectivity. One of the stereocenters was installed using a configurationally labile lithiated primary benzyl benzoate, resulting in high levels of substrate‐controlled (undesired) diastereoselectivity. However, reversal of selectivity was achieved by using a novel diastereoselective Matteson homologation. Stereospecific alkynylation of a hindered secondary benzylic boronic ester enabled completion of the synthesis in a total of eight steps.
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spelling pubmed-52154352017-01-18 Short Enantioselective Total Synthesis of Tatanan A and 3‐epi‐Tatanan A Using Assembly‐Line Synthesis Noble, Adam Roesner, Stefan Aggarwal, Varinder K. Angew Chem Int Ed Engl Communications Short and highly stereoselective total syntheses of the sesquilignan natural product tatanan A and its C3 epimer are described. An assembly‐line synthesis approach, using iterative lithiation–borylation reactions, was applied to install the three contiguous stereocenters with high enantio‐ and diastereoselectivity. One of the stereocenters was installed using a configurationally labile lithiated primary benzyl benzoate, resulting in high levels of substrate‐controlled (undesired) diastereoselectivity. However, reversal of selectivity was achieved by using a novel diastereoselective Matteson homologation. Stereospecific alkynylation of a hindered secondary benzylic boronic ester enabled completion of the synthesis in a total of eight steps. John Wiley and Sons Inc. 2016-11-16 2016-12-19 /pmc/articles/PMC5215435/ /pubmed/27865037 http://dx.doi.org/10.1002/anie.201609598 Text en © 2016 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. This is an open access article under the terms of the Creative Commons Attribution (http://creativecommons.org/licenses/by/4.0/) License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.
spellingShingle Communications
Noble, Adam
Roesner, Stefan
Aggarwal, Varinder K.
Short Enantioselective Total Synthesis of Tatanan A and 3‐epi‐Tatanan A Using Assembly‐Line Synthesis
title Short Enantioselective Total Synthesis of Tatanan A and 3‐epi‐Tatanan A Using Assembly‐Line Synthesis
title_full Short Enantioselective Total Synthesis of Tatanan A and 3‐epi‐Tatanan A Using Assembly‐Line Synthesis
title_fullStr Short Enantioselective Total Synthesis of Tatanan A and 3‐epi‐Tatanan A Using Assembly‐Line Synthesis
title_full_unstemmed Short Enantioselective Total Synthesis of Tatanan A and 3‐epi‐Tatanan A Using Assembly‐Line Synthesis
title_short Short Enantioselective Total Synthesis of Tatanan A and 3‐epi‐Tatanan A Using Assembly‐Line Synthesis
title_sort short enantioselective total synthesis of tatanan a and 3‐epi‐tatanan a using assembly‐line synthesis
topic Communications
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5215435/
https://www.ncbi.nlm.nih.gov/pubmed/27865037
http://dx.doi.org/10.1002/anie.201609598
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