1606173-73-2Relevant academic research and scientific papers
CATALYSTS FOR EFFICIENT Z-SELECTIVE METATHESIS
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Paragraph 00676; 00684; 00693-00696; 00736-00737, (2015/01/09)
The present application provides, among other things, compounds and methods for metathesis reactions. In some embodiments, provided compounds promote highly efficient and highly Z-selective metathesis. In some embodiments, provided compounds and methods are particularly useful for producing allyl alcohols. In some embodiments, provided compounds have the structure of formula I. In some embodiments, provided compounds comprise ruthenium, and a ligand bonded to ruthenium through a sulfur atom.
Broadly applicable Z- and diastereoselective ring-opening/cross-metathesis catalyzed by a dithiolate Ru complex
Koh, Ming Joo,Khan, R. Kashif M.,Torker, Sebastian,Hoveyda, Amir H.
supporting information, p. 1968 - 1972 (2014/03/21)
A broadly applicable Ru-catalyzed protocol for Z-selective ring-opening/cross-metathesis (ROCM) is disclosed. In addition to reactions relating to terminal alkenes of different sizes, the first examples of Z-selective ROCM processes involving heteroaryl olefins, 1,3-dienes, and O- and S-substituted alkenes as well as allylic and homoallylic alcohols are reported. Z-Selective transformations with an α-substituted allylic alcohol are shown to afford congested Z 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, >98:2 Z/E, and >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. Finally, the full range: For the first time, Ru-catalyzed olefin metathesis transformations with heteroaryl-substituted alkenes, 1,3-dienes, enol ethers, and allylic and homoallylic alcohols can be performed efficiently and often with >98 % Z selectivity. Hydrogen bonding with the dithiolate ligand likely facilitates ring-opening/cross-metathesis reactions of allylic alcohols. Copyright
