Broadly Applicable Z‐ and Diastereoselective Ring‐Opening/Cross‐Metathesis Catalyzed by a Dithiolate Ru Complex1. (29th January 2014)

• Record Type: Journal Article
• Authors: Koh, Ming Joo; Khan, R. Kashif M.; Torker, Sebastian; Hoveyda, Amir H.
• Is Part Of: Angewandte Chemie. Volume 126:Number 7(2014)
• Page Start: 1999
• Page End: 2003
• Publication Date: 2014-01-29
• Subjects: Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.201309430
• Languages: English
• ISSNs: 0044-8249

Abstract

<abstract abstract-type="main" xml:lang="en"> <title>Abstract</title> <p>A broadly applicable Ru‐catalyzed protocol for <italic>Z</italic>‐selective ring‐opening/cross‐metathesis (ROCM) is disclosed. In addition to reactions relating to terminal alkenes of different sizes, the first examples of <italic>Z</italic>‐selective ROCM processes involving heteroaryl olefins, 1, 3‐dienes, and O‐ and S‐substituted alkenes as well as allylic and homoallylic alcohols are reported. <italic>Z</italic>‐Selective transformations with an α‐substituted allylic alcohol are shown to afford congested <italic>Z</italic> alkenes with high diastereoselectivity. Transformations are performed in the presence of 2.0–5.0 mol % of a recently disclosed Ru‐based dithiolate complex that can be easily prepared in a single step from commercially available starting materials. Typically, transformations proceed at ambient temperature and are complete within eight hours; products are obtained in up to 97 % yield, &gt;98:2 <italic>Z</italic>/<italic>E</italic>, and &gt;98:2 diastereomeric ratio. The present investigations reveal a mechanistically significant attribute of the Ru‐based dithiolates that arises from electrostatic interactions with anionic S‐based ligands.</p> </abstract>