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Broadly Applicable Z ‐ and Diastereoselective Ring‐Opening/Cross‐Metathesis Catalyzed by a Dithiolate Ru Complex
Author(s) -
Koh Ming Joo,
Khan R. Kashif M.,
Torker Sebastian,
Hoveyda Amir H.
Publication year - 2014
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201309430
Subject(s) - allylic rearrangement , diastereomer , metathesis , chemistry , catalysis , ring (chemistry) , yield (engineering) , medicinal chemistry , alcohol , combinatorial chemistry , salt metathesis reaction , stereochemistry , organic chemistry , polymerization , materials science , polymer , metallurgy
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.