Highly active chiral ruthenium catalysts for asymmetric ring-closing olefin metathesis.
The synthesis of olefin metathesis catalysts containing chiral, monodentate N-heterocyclic carbenes and their application to asymmetric ring-closing metathesis (ARCM) are reported. These catalysts retain the high levels of reactivity found in the related achiral variants (1a and 1b). Using the parent chiral catalysts 2a and 2b and derivatives that contain steric bulk in the meta positions of the N-bound aryl rings (catalysts 3-5), five- through seven-membered rings were formed in up to 92% ee. The addition of sodium iodide to catalysts 2a-4a (to form 2b-4b in situ) caused a dramatic increase in enantioselectivity for many substrates. Catalyst 5a, which gave high enantiomeric excesses for certain substrates without the addition of NaI, could be used in loadings of < or =1 mol %. Mechanistic explanations for the large sodium iodide effect as well as possible mechanistic pathways leading to the observed products are discussed.
Funk
Timothy W
TW
Arnold and Mabel Beckman Laboratory of Chemical Synthesis, Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, CA 91125, USA.
Berlin
Jacob M
JM
Grubbs
Robert H
RH
D000475:Alkenes / Q000737:chemistry*; D002384:Catalysis; D003500:Cyclization; D004988:Ethers, Cyclic / Q000138:chemical synthesis*; D009942:Organometallic Compounds / Q000737:chemistry; D012428:Ruthenium / Q000737:chemistry*; D013237:Stereoisomerism
D000475:Alkenes; D004988:Ethers, Cyclic; D009942:Organometallic Compounds; D012428:Ruthenium