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A Highly Efficient Synthesis of Z-Macrocycles using Stereoretentive, Ruthenium-Based Metathesis Catalysts

Ahmed, Tonia S. and Grubbs, Robert H. (2017) A Highly Efficient Synthesis of Z-Macrocycles using Stereoretentive, Ruthenium-Based Metathesis Catalysts. Angewandte Chemie International Edition, 56 (37). pp. 11213-11216. ISSN 1433-7851. https://resolver.caltech.edu/CaltechAUTHORS:20170627-070258441

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Abstract

A highly efficient, Z-selective ring-closing metathesis system for the formation of macrocycles using a stereoretentive, ruthenium-based catalyst supported by a dithiolate ligand is reported. The catalyst is remarkably active as observed in initiation experiments showing complete catalyst initiation at −20 °C within 10 minutes. Macrocyclization reactions generated Z-products from easily accessible diene starting materials bearing a Z-olefin moiety. This approach provides a more efficient and selective route to Z-macrocycles relative to previously reported systems. Reactions were completed within shorter reaction times, and turnover numbers of up to 100 could be achieved. Macrocyclic lactones ranging in size from twelve- to seventeen-membered rings were synthesized in moderate to high yields (67–79 %) with excellent Z-selectivity (95–99 %).


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1002/anie.201704670DOIArticle
http://onlinelibrary.wiley.com/doi/10.1002/anie.201704670/abstractPublisherArticle
http://onlinelibrary.wiley.com/doi/10.1002/anie.201704670/suppinfoPublisherSupporting Information
ORCID:
AuthorORCID
Grubbs, Robert H.0000-0002-0057-7817
Additional Information:© 2017 Wiley. Manuscript received: May 5, 2017; Accepted manuscript online: June 23, 2017; Version of record online: July 12, 2017. Funding from the Office of Naval Research (N00014-14-1-0650), NIH (GM031332), and NSF (CHE-1502616) is acknowledged. T.S.A. recognizes NSF for support through a Graduate Research Fellowship. Any opinions, findings, and conclusions or recommendations expressed in this material are those of the authors and do not necessarily reflect the views of the National Science Foundation. The authors would like to thank M. A. Pribisko, W. J. Wolf, C. W. Lee, T. P. Montgomery, and N. F. Nathel for helpful suggestions. D. Vandervelde and W. J. Wolf are acknowledged for their help with initiation experiments. N. Torian and M. Shahgholi are thanked for their assistance with high-resolution mass spectrometry. Materia, Inc. is acknowledged for generous donations of 4. The authors declare no conflict of interest.
Funders:
Funding AgencyGrant Number
Office of Naval Research (ONR)N00014-14-1-0650
NIHGM031332
NSFCHE-1502616
NSF Graduate Research FellowshipUNSPECIFIED
Subject Keywords:macrocycle, metathesis, Z-selective, stereoretentive, ruthenium
Issue or Number:37
Record Number:CaltechAUTHORS:20170627-070258441
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20170627-070258441
Official Citation:T. S. Ahmed, R. H. Grubbs, Angew. Chem. Int. Ed. 2017, 56, 11213
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:78586
Collection:CaltechAUTHORS
Deposited By: Ruth Sustaita
Deposited On:27 Jun 2017 19:53
Last Modified:03 Oct 2019 18:09

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