Highly diastereoselective formation of 3, 7-dioxabicyclo[3.3.0]octan-2-ones in reaction of 2-arylcyclopropanedicarboxylates with aromatic aldehydes using 1, 2-zwitterionic reactivity type. Issue 38 (20th September 2017)

• Record Type: Journal Article
• Authors: Borisov, Denis D.; Novikov, Roman A.; Tomilov, Yury V.
• Is Part Of: Tetrahedron letters. Volume 58:Issue 38(2017)
• Page Start: 3712
• Page End: 3716
• Publication Date: 2017-09-20
• Subjects: Donor-acceptor cyclopropanes -- Aromatic aldehydes -- 1, 2-Zwitterion -- Gallium trichloride -- Dioxabicyclo[3.3.0]octan-2-ones; Chemistry, Organic -- Periodicals; 547.005
• DOI: 10.1016/j.tetlet.2017.08.025
• Languages: English
• ISSNs: 0040-4039

Abstract

Graphical abstract: Highlights: A new reaction of D-A cyclopropanes with aromatic aldehydes has been developed. Our approach is based on 1, 2-zwitterionic type of reactivity mediated by GaCl3 . The process results in the 3, 7-dioxabicyclo[3.3.0]octane skeleton. The reaction is a complex anionic-cationic cascade process. Two C–C and two C–O bonds, as well as five stereocenters, are formed. Abstract: A new reaction of 2-arylcyclopropane-1, 1-dicarboxylates (ACDC) with aromatic aldehydes that occurs via generation of a 1, 2-zwitterionic intermediate in the presence of GaCl3 has been developed. This process results in the 3, 7-dioxabicyclo[3.3.0]octane frame by addition of two aldehyde molecules to an ACDC molecule. The reaction is a complex anionic-cationic cascade process involving the formation of two C–C bonds, two C–O bonds, and five stereocenters. The process occurs with high diastereoselectivity to give only one diastereomer. A probable reaction mechanism is suggested and confirmed by NMR monitoring data.