Rhodium‐Catalyzed Enantioselective Defluorinative α‐Arylation of Secondary Amides. Issue 49 (8th November 2018)

• Record Type: Journal Article
• Authors: Jang, Young Jin; Rose, Daniel; Mirabi, Bijan; Lautens, Mark
• Is Part Of: Angewandte Chemie international edition. Volume 57:Issue 49(2018)
• Page Start: 16147
• Page End: 16151
• Publication Date: 2018-11-08
• Subjects: asymmetric catalysis -- defluorinative arylation -- rhodium catalysis; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201808509
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: We exploited the reactivity of an electronically biased Michael acceptor to perform a defluorinative α‐arylation reaction using a chiral diene(L*)‐rhodium catalyst. Through this methodology, we are able to obtain various secondary amides, containing a tertiary α‐stereocenter and a β, γ‐unsaturated gem ‐difluoro olefin, with excellent enantioselectivities. This methodology addresses the limitations of the previously described α‐arylation methods to construct stereo‐labile tertiary α‐stereocenters. Further investigation of the reaction via in situ 19 F NMR monitoring suggests that the formation of the product leads to the inhibition of the active rhodium catalyst. Abstract : Rhodium catalysis : The reactivity of an electronically biased Michael acceptor to perform a defluorinative α‐arylation reaction using a chiral diene(L*)‐rhodium catalyst is described. Through this methodology, various secondary amides, containing a tertiary α‐stereocenter and a β, γ‐unsaturated gem ‐difluoro olefin, with excellent enantioselectivities are obtainable.