The significance of degenerate processes to enantioselective olefin metathesis reactions promoted by stereogenic-at-Mo complexes.
The present study provides spectroscopic and experimental evidence demonstrating that degenerate metathesis is critical to the effectiveness of this emerging class of chiral catalysts. Isolation and X-ray characterization of both diastereomeric complexes, as well as an examination of the reactivity and enantioselectivity patterns exhibited by such initiating neophylidenes in promoting ring-closing metathesis processes, are disclosed. Only when sufficient amounts of ethylene are generated and inversion at Mo through degenerate processes occurs at a sufficiently rapid rate is high enantioselectivity achieved, irrespective of the stereochemical identity of the initiating alkylidene (Curtin-Hammett kinetics). With diastereomeric metal complexes that undergo rapid interconversion, stereomutation at the metal center becomes inconsequential, and stereoselective synthesis of a chiral catalyst is not required.
Meek
Simon J
SJ
Department of Chemistry, Merkert Chemistry Center, Boston College, Chestnut Hill, Massachusetts 02467, USA.
Malcolmson
Steven J
SJ
Li
Bo
B
Schrock
Richard R
RR
Hoveyda
Amir H
AH
D000475:Alkenes / Q000737:chemistry*; D018360:Crystallography, X-Ray; D008958:Models, Molecular; D015394:Molecular Structure; D008982:Molybdenum / Q000737:chemistry*; D009942:Organometallic Compounds / Q000737:chemistry*; D013237:Stereoisomerism
D000475:Alkenes; D009942:Organometallic Compounds; D008982:Molybdenum