Using stereoretention for the synthesis of <i>E</i>-macrocycles with ruthenium-based olefin metathesis catalysts

Abstract

The synthesis of <i>E</i>-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 <b>4</b> providing meaningful yields of products in much shorter reaction times than stereoretentive catalysts <b>2</b> and <b>3</b>. Macrocycles were generated with excellent selectivity (>99% <i>E</i>) and in moderate to high yields (47-80% yield) from diene starting materials bearing two <i>E</i>-configured olefins. A variety of rings were constructed, ranging from 12- to 18-membered macrocycles, including the antibiotic recifeiolide.