Preparation of Macrocyclic Z-Enoates and (E,Z)- or (Z,E)-Dienoates through Catalytic Stereoselective Ring-Closing Metathesis

[Image: see text] The first examples of catalyst-controlled stereoselective macrocyclic ring-closing metathesis reactions that generate Z-enoates as well as (E,Z)- or (Z,E)-dienoates are disclosed. Reactions promoted by 3.0–10 mol % of a Mo-based monoaryloxide pyrrolide complex proceed to completion...

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Autores principales: Zhang, Hanmo, Yu, Elsie C., Torker, Sebastian, Schrock, Richard R., Hoveyda, Amir H.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2014
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC4270125/
https://www.ncbi.nlm.nih.gov/pubmed/25402822
http://dx.doi.org/10.1021/ja510768c
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author Zhang, Hanmo
Yu, Elsie C.
Torker, Sebastian
Schrock, Richard R.
Hoveyda, Amir H.
author_facet Zhang, Hanmo
Yu, Elsie C.
Torker, Sebastian
Schrock, Richard R.
Hoveyda, Amir H.
author_sort Zhang, Hanmo
collection PubMed
description [Image: see text] The first examples of catalyst-controlled stereoselective macrocyclic ring-closing metathesis reactions that generate Z-enoates as well as (E,Z)- or (Z,E)-dienoates are disclosed. Reactions promoted by 3.0–10 mol % of a Mo-based monoaryloxide pyrrolide complex proceed to completion within 2–6 h at room temperature. The desired macrocycles are formed in 79:21 to >98:2 Z/E selectivity; stereoisomerically pure products can be obtained in 43–75% yield after chromatography. Utility is demonstrated by application to a concise formal synthesis of the natural product (+)-aspicilin.
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spelling pubmed-42701252014-12-18 Preparation of Macrocyclic Z-Enoates and (E,Z)- or (Z,E)-Dienoates through Catalytic Stereoselective Ring-Closing Metathesis Zhang, Hanmo Yu, Elsie C. Torker, Sebastian Schrock, Richard R. Hoveyda, Amir H. J Am Chem Soc [Image: see text] The first examples of catalyst-controlled stereoselective macrocyclic ring-closing metathesis reactions that generate Z-enoates as well as (E,Z)- or (Z,E)-dienoates are disclosed. Reactions promoted by 3.0–10 mol % of a Mo-based monoaryloxide pyrrolide complex proceed to completion within 2–6 h at room temperature. The desired macrocycles are formed in 79:21 to >98:2 Z/E selectivity; stereoisomerically pure products can be obtained in 43–75% yield after chromatography. Utility is demonstrated by application to a concise formal synthesis of the natural product (+)-aspicilin. American Chemical Society 2014-11-17 2014-11-26 /pmc/articles/PMC4270125/ /pubmed/25402822 http://dx.doi.org/10.1021/ja510768c Text en Copyright © 2014 American Chemical Society This is an open access article published under an ACS AuthorChoice License (http://pubs.acs.org/page/policy/authorchoice_termsofuse.html) , which permits copying and redistribution of the article or any adaptations for non-commercial purposes.
spellingShingle Zhang, Hanmo
Yu, Elsie C.
Torker, Sebastian
Schrock, Richard R.
Hoveyda, Amir H.
Preparation of Macrocyclic Z-Enoates and (E,Z)- or (Z,E)-Dienoates through Catalytic Stereoselective Ring-Closing Metathesis
title Preparation of Macrocyclic Z-Enoates and (E,Z)- or (Z,E)-Dienoates through Catalytic Stereoselective Ring-Closing Metathesis
title_full Preparation of Macrocyclic Z-Enoates and (E,Z)- or (Z,E)-Dienoates through Catalytic Stereoselective Ring-Closing Metathesis
title_fullStr Preparation of Macrocyclic Z-Enoates and (E,Z)- or (Z,E)-Dienoates through Catalytic Stereoselective Ring-Closing Metathesis
title_full_unstemmed Preparation of Macrocyclic Z-Enoates and (E,Z)- or (Z,E)-Dienoates through Catalytic Stereoselective Ring-Closing Metathesis
title_short Preparation of Macrocyclic Z-Enoates and (E,Z)- or (Z,E)-Dienoates through Catalytic Stereoselective Ring-Closing Metathesis
title_sort preparation of macrocyclic z-enoates and (e,z)- or (z,e)-dienoates through catalytic stereoselective ring-closing metathesis
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC4270125/
https://www.ncbi.nlm.nih.gov/pubmed/25402822
http://dx.doi.org/10.1021/ja510768c
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