1. Chiral cyclopentadienylruthenium sulfoxide catalysts for asymmetric redox bicycloisomerization
- Author
-
Meera Rao, Michael C. Ryan, and Barry M. Trost
- Subjects
sulfoxide ,Alkyne ,010402 general chemistry ,01 natural sciences ,Full Research Paper ,lcsh:QD241-441 ,ruthenium catalysis ,chemistry.chemical_compound ,Cycloisomerization ,lcsh:Organic chemistry ,cycloisomerization ,Moiety ,Organic chemistry ,lcsh:Science ,[4.1.0] bicycles ,chemistry.chemical_classification ,010405 organic chemistry ,Organic Chemistry ,Enantioselective synthesis ,asymmetric catalysis ,1,7-enyne ,Sulfoxide ,Combinatorial chemistry ,Cycloaddition ,0104 chemical sciences ,3. Good health ,Sulfonamide ,Chemistry ,1,6-enyne ,chemistry ,Propargyl ,lcsh:Q ,[3.1.0] bicycles - Abstract
A full account of our efforts toward an asymmetric redox bicycloisomerization reaction is presented in this article. Cyclopentadienylruthenium (CpRu) complexes containing tethered chiral sulfoxides were synthesized via an oxidative [3 + 2] cycloaddition reaction between an alkyne and an allylruthenium complex. Sulfoxide complex 1 containing a p-anisole moiety on its sulfoxide proved to be the most efficient and selective catalyst for the asymmetric redox bicycloisomerization of 1,6- and 1,7-enynes. This complex was used to synthesize a broad array of [3.1.0] and [4.1.0] bicycles. Sulfonamide- and phosphoramidate-containing products could be deprotected under reducing conditions. Catalysis performed with enantiomerically enriched propargyl alcohols revealed a matched/mismatched effect that was strongly dependent on the nature of the solvent.
- Published
- 2016