Enantioselective Synthesis of Spiro‐oxiranes: An Asymmetric Addition/Aldol/Spirocyclization Domino Cascade. (18th August 2021)

• Record Type: Journal Article
• Authors: Choo, Ken‐Loon; Mirabi, Bijan; Demmans, Karl Z.; Lautens, Mark
• Is Part Of: Angewandte Chemie. Volume 133:Number 39(2021)
• Page Start: 21359
• Page End: 21364
• Publication Date: 2021-08-18
• Subjects: asymmetric catalysis -- enantioselectivity -- rhodium -- spiro compounds; Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.202105562
• Languages: English
• ISSNs: 0044-8249

Abstract

Abstract: Enantioenriched spiro‐oxiranes bearing three contiguous stereocenters were synthesized using a rhodium‐catalyzed asymmetric addition/aldol/spirocyclization sequence. Starting from a linear substrate, the cascade enabled the formation of a spirocyclic framework in a single step. sp 2 ‐ and sp‐hybridized carbon nucleophiles were found to be competent initiators for this cascade, giving arylated or alkynylated products, respectively. Derivatization studies demonstrated the synthetic versatility of both the epoxide and the alkyne moieties of the products. DFT calculations were used to reconcile spectroscopic discrepancies observed between the solution‐ and solid‐state structures of the products. Abstract : A rhodium‐catalyzed asymmetric addition/aldol/spirocyclization domino cascade to generate spiro‐oxiranes is reported. sp 2 ‐ and sp‐hybridized carbon nucleophiles are used to initiate the cascade to give arylated and alkynylated products.