Using stereoretention for the synthesis of E-macrocycles with ruthenium-based olefin metathesis catalysts

Abstract

The synthesis of E-macrocycles is achieved using stereoretentive, Ru-based olefin metathesis catalysts supported by dithiolate ligands. Kinetic studies elucidate marked differences in activity among the catalysts tested, with catalyst 4 providing meaningful yields of products in much shorter reaction times than stereoretentive catalysts 2 and 3. Macrocycles were generated with excellent selectivity (>99% E) and in moderate to high yields (47–80% yield) from diene starting materials bearing two E-configured olefins. A variety of rings were constructed, ranging from 12- to 18-membered macrocycles, including the antibiotic recifeiolide.

Additional Information

© 2018 The Royal Society of Chemistry. This Open Access Article is licensed under a Creative Commons Attribution-Non Commercial 3.0 Unported Licence. Received 27th January 2018, Accepted 27th February 2018, First published on 14th March 2018. The authors acknowledge funding from the Office of Naval Research (N00014-14-1-0650), NIH (GM031332), and NSF (CHE-1502616). T. S. A. recognizes NSF for support through a Graduate Research Fellowship. T. P. M. would like to acknowledge the Arnold and Mabel Beckman Foundation for funding. The authors would like to thank W. J. Wolf, C. Xu, C. W. Lee, J. Li, and N. F. Nathel for helpful suggestions. N. Torian and M. Shahgholi are thanked for their help with high-resolution mass spectrometry. Materia, Inc. is acknowledged for generous donations of Ru catalyst precursors. Conflicts of interest: There are no conflicts to declare.

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Supplemental Material - c8sc00435h1_si.pdf

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