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Rhodium‐Catalyzed Enantioselective Defluorinative α‐Arylation of Secondary Amides
Author(s) -
Jang Young Jin,
Rose Daniel,
Mirabi Bijan,
Lautens Mark
Publication year - 2018
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201808509
Subject(s) - stereocenter , rhodium , enantioselective synthesis , catalysis , olefin fiber , chemistry , reactivity (psychology) , acceptor , diene , organic chemistry , combinatorial chemistry , medicine , natural rubber , condensed matter physics , physics , alternative medicine , pathology
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.