Insights into the Mechanism of Enantioselective Copper‐Catalyzed Ring‐Opening Allylic Alkylation of Cyclopropanols. Issue 11 (27th April 2022)

• Record Type: Journal Article
• Authors: Kitabayashi, Akito; Mizushima, Sho; Higashida, Kosuke; Yasuda, Yuto; Shimizu, Yohei; Sawamura, Masaya
• Is Part Of: Advanced synthesis & catalysis. Volume 364:Issue 11(2022)
• Page Start: 1855
• Page End: 1862
• Publication Date: 2022-04-27
• Subjects: Copper Catalyst -- Asymmetric Allylic Alkylation -- Homoenolate -- DFT Calculations -- Noncovalent Interactions; Catalysis -- Periodicals; Organic compounds -- Synthesis -- Periodicals; Chemistry -- Periodicals; Chemistry, Technical -- Periodicals; Chemistry -- Periodicals; Catalysis -- Periodicals; Technology, Pharmaceutical -- Periodicals; 547.2
• DOI: 10.1002/adsc.202200157
• Languages: English
• ISSNs: 1615-4150

Abstract

Abstract: Enantioselective copper‐catalyzed ring‐opening allylic alkylation of a cyclopropanol with an allyl phosphate was developed using a phenol‐NHC chiral ligand. DFT calculations indicated that a copper homoenolate is formed via Li−Cu bimetallic activation of a cyclopropoxide and that syn ‐SN 2' attack of the Cu center of the homoenolate to the allyl phosphate followed by facile C−C bond formation affords the β‐allylated ketone. Noncovalent interaction analysis showed that the enantiocontrol is achieved by the synergy of electrostatic interactions among Cu, Li, and O atoms, C−H⋅⋅⋅O interactions, and C−H/π London dispersions. Abstract :