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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. [ABSTRACT FROM AUTHOR]

Reported herein is the rhodium(III)‐catalyzed C−H activation of anilines bearing an N‐isoquinolyl directing group for oxidative [3+2] annulation with four classes of internal alkynes, leading to atroposelective indole synthesis via dynamic kinetic annulation with C‐N reductive elimination constituting the stereo‐determining step. This reaction proceeds under mild conditions with high regio‐ and enantioselectivity and functional group compatibility. [ABSTRACT FROM AUTHOR]

Axial‐to‐central chirality transfer is an important strategy to construct chiral centers, where the axially chiral reagents are mostly limited to atropomerically stable ones. Reported herein is a RhIII‐catalyzed enantioselective spiroannulative synthesis of nitrones. The coupling proceeds via C−H arylation to give an atropomerically metastable biaryl, followed by intramolecular dearomative trapping under oxidative conditions with high degree of chirality transfer. [ABSTRACT FROM AUTHOR]

Previous direct C−H nitrogenation suffered from simple amidation/amination with limited atom-economy and is mostly limited to C(sp2)−H substrates. In this work, anthranil was designed as a novel bifunctional aminating reagent for both C(sp2)−H and C(sp3)−H bonds under rhodium(III) catalysis, thus affording a nucleophilic aniline tethered to an electrophilic carbonyl. A tridendate rhodium(III) complex has been isolated as the resting state of the catalyst, and DFT studies established the intermediacy of a nitrene species. [ABSTRACT FROM AUTHOR]