Intriguing Electrophilic Reactivity of Donor–Acceptor Cyclopropanes: Experimental and Theoretical Studies. Issue 35 (19th September 2017)

• Record Type: Journal Article
• Authors: Dousset, Maxime; Parrain, Jean‐Luc; Chouraqui, Gaëlle
• Is Part Of: European journal of organic chemistry. Issue 35(2017)
• Page Start: 5238
• Page End: 5245
• Publication Date: 2017-09-19
• Subjects: Donor–acceptor systems -- Cyclopropanes -- Zwitterions -- Reaction mechanisms -- Density functional calculations; Chemistry, Organic -- Periodicals; Organic compounds -- Synthesis -- Periodicals; Bioorganic chemistry -- Periodicals; Chemistry, Physical organic -- Periodicals; 547
• DOI: 10.1002/ejoc.201701058
• Languages: English
• ISSNs: 1434-193X

Abstract

Abstract : A new reactivity of donor–acceptor cyclopropanes (DACs) has been highlighted and, for the first time, we report that they could formally behave as nucleophiles and be functionalized at their C3 position. The donor–acceptor cyclopropane acts as a formal nucleophilic synthetic equivalent of a 1, 2‐zwitterion and could be described as an umpolung synthon. A highly substituted lactone is reached, and even more impressive is the formation of four stereogenic centers with complete control of their relative configuration. Both experimental and computational studies were performed to provide an overall picture of the mechanism. Abstract : A new reactivity of donor–acceptor cyclopropanes (DACs) has been highlighted. They could formally act as nucleophiles and be functionalized at their C3 position. A highly substituted lactone is reached with the formation of four stereogenic centers with complete control of their relative configuration. Experimental and computational studies provide an overall picture of the mechanism.