Reported herein is the rhodium(III)-catalyzed C À 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. Scheme 1. Metal-Catalyzed Synthesis of Axially Chiral Indoles.
An efficient and practical synthesis of isoindolo[2,1‐b]isoquinoline‐5,7‐diones through Pd‐catalyzed C−H activation/carbonylative annulation of isoquinolones with CO (1 atm) is presented. Deuterium‐labeling experiments revealed that the aryl C(sp2)−H bond activation might be the rate‐determining step. More interestingly, the title compounds could also be prepared directly from the cascade reaction of N‐methoxy benzamides and internal alkynes, as the precursors of isoquinolones, under an atmospheric pressure of carbon monoxide through a Rh/Pd relay catalysis in a user‐friendly manner.magnified image
Rh(III)-catalyzed
site-selective oxidative spirocyclization reactions of isoquinolones
with α-diazo-1,3-indandiones leading to three kinds of spiro
compounds by employing isoquinolones with different structural features
or tuning the reaction parameters are presented. In addition, a plausible
catalytic cycle is proposed on the basis of control experimental results
and density functional theory calculations. Finally, the diverse transformations
of the spiro products into other complex skeletons demonstrate the
synthetic utility of this protocol.
Chiral RhIII catalysts can catalyze the asymmetric [4+1] spiroannulation of O-pivaloyl oximes with α-diazo homophthalimides under redox-neutral and acid/base-neutral conditions, leading to formation of chiral spirocyclic imines as a result...
Rhodium-catalyzed diverse tandem twofold C-H bond activation reactions of para olefin-tethered arenes have been realized, with unsaturated reagents such as internal alkynes, dioxazolones, and isocyanates being the coupling partner as...
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