Angewandte Chemie - International Edition p. 1968 - 1972 (2014)
Update date:2022-07-29
Topics:
Koh, Ming Joo
Khan, R. Kashif M.
Torker, Sebastian
Hoveyda, Amir H.
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
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Doi:10.1021/jo402586v
(2014)Doi:10.1002/ejoc.201900117
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(2014)