Catalytic Asymmetric Ring-Opening Metathesis/Cross Metathesis (AROM/CM) Reactions. Mechanism and Application to Enantioselective Synthesis of Functionalized Cyclopentanes

• Published in: Journal of the American Chemical Society 2001-08, Vol.123 (32), p.7767-7778
• Main Authors: La, Daniel S, Sattely, Elizabeth S, Ford, J. Gair, Schrock, Richard R, Hoveyda, Amir H
• Format: Article
• Language: English
• Subjects: Alkenes - chemistry; Catalysis; Cyclopentanes - chemical synthesis; Cyclopentanes - isolation & purification; Ethers - chemistry; Models, Chemical; Norbornanes - chemistry; Stereoisomerism; Styrenes - chemistry
• ISSN: 0002-7863; 1520-5126
• DOI: 10.1021/ja010684q

Studies regarding the first examples of catalytic asymmetric ring-opening metathesis (AROM) reactions are detailed. This enantioselective cleavage of norbornyl alkenes is followed by an intermolecular cross metathesis with a terminal olefin partner; judicious selection of olefin is required so that oligomerization and dimerization side products are avoided. Results outlined herein suggest that the presence of suitably positioned heteroatom substituents may be critical to reaction efficiency. Mo-catalyzed tandem AROM/CM affords functionalized cyclopentyl dienes in >98% ee and >98% trans olefin selectivity; both secondary and tertiary ether products can be obtained. The examples provided include the catalytic synthesis of an optically pure cyclopentyl epoxide and dimethyl acetal. Mechanistic studies suggest that it is the more substituted benzylidene or silylated alkylidenes that are involved in the catalytic process (vs the corresponding Mo-methylidenes). Although electron rich benzylidenes react more efficiently, the derived electron poor Mo complexes promote AROM/CM transformations as well; alkylidenes that bear a boron substituent are unreactive.