Rhodium-Catalyzed Atroposelective Access to Axially Chiral Olefins via C−H Bond Activation and Directing Group Migration
Ruijie Mi
School of Chemistry and Chemical Engineering, Shaanxi Normal University (SNNU), Xi'an, 710062 China
Search for more papers by this authorHaohua Chen
School of Chemistry and Chemical Engineering, Chongqing University, Chongqing, 400030 China
Search for more papers by this authorDr. Xukai Zhou
Department of Chemistry, The University of Chicago, Chicago, IL, 60637 USA
Search for more papers by this authorProf. Dr. Nan Li
School of Chemistry and Chemical Engineering, Shaanxi Normal University (SNNU), Xi'an, 710062 China
Search for more papers by this authorDanqing Ji
School of Chemistry and Chemical Engineering, Shaanxi Normal University (SNNU), Xi'an, 710062 China
Search for more papers by this authorCorresponding Author
Dr. Fen Wang
School of Chemistry and Chemical Engineering, Shaanxi Normal University (SNNU), Xi'an, 710062 China
Search for more papers by this authorProf. Dr. Yu Lan
School of Chemistry and Chemical Engineering, Chongqing University, Chongqing, 400030 China
Search for more papers by this authorCorresponding Author
Prof. Dr. Xingwei Li
School of Chemistry and Chemical Engineering, Shaanxi Normal University (SNNU), Xi'an, 710062 China
Institute of Molecular Science and Engineering, Institute of Frontier and Interdisciplinary Sciences, Shandong University, Qingdao, 266237 China
Search for more papers by this authorRuijie Mi
School of Chemistry and Chemical Engineering, Shaanxi Normal University (SNNU), Xi'an, 710062 China
Search for more papers by this authorHaohua Chen
School of Chemistry and Chemical Engineering, Chongqing University, Chongqing, 400030 China
Search for more papers by this authorDr. Xukai Zhou
Department of Chemistry, The University of Chicago, Chicago, IL, 60637 USA
Search for more papers by this authorProf. Dr. Nan Li
School of Chemistry and Chemical Engineering, Shaanxi Normal University (SNNU), Xi'an, 710062 China
Search for more papers by this authorDanqing Ji
School of Chemistry and Chemical Engineering, Shaanxi Normal University (SNNU), Xi'an, 710062 China
Search for more papers by this authorCorresponding Author
Dr. Fen Wang
School of Chemistry and Chemical Engineering, Shaanxi Normal University (SNNU), Xi'an, 710062 China
Search for more papers by this authorProf. Dr. Yu Lan
School of Chemistry and Chemical Engineering, Chongqing University, Chongqing, 400030 China
Search for more papers by this authorCorresponding Author
Prof. Dr. Xingwei Li
School of Chemistry and Chemical Engineering, Shaanxi Normal University (SNNU), Xi'an, 710062 China
Institute of Molecular Science and Engineering, Institute of Frontier and Interdisciplinary Sciences, Shandong University, Qingdao, 266237 China
Search for more papers by this authorGraphical Abstract
Two classes of tetrasubstituted axially chiral olefins have been accessed in excellent enantioselectivity via RhIII-catalyzed asymmetric C−H activation assisted by a migratable directing group.
Abstract
Axially chiral open-chain olefins represent an underexplored class of chiral platform. In this report, two classes of tetrasubstituted axially chiral acyclic olefins have been accessed in excellent enantioselectivity and regioselectivity via C−H activation of (hetero)arenes assisted by a migratable directing group en route to coupling with sterically hindered alkynes. The coupling of indoles bearing an N-aminocarbonyl directing group afforded C–N axially chiral acrylamides with the assistance of a racemic zinc carboxylate additive. DFT studies suggest a β-nitrogen elimination–reinsertion pathway for the directing group migration. Meanwhile, the employment of N-phenoxycarboxamide delivered C−C axially chiral enamides via migration of the oxidizing directing group. Experiments suggest that in both cases the (hetero)arene substrate adopts a well-defined orientation during the C−H activation, which in turn determines the disposition of the alkyne in migratory insertion. Synthetic applications of representative chiral olefins are demonstrated.
Conflict of interest
The authors declare no conflict of interest.
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