Rhodium(III)-Catalyzed Enantio- and Diastereoselective C-H Cyclopropylation of N-Phenoxylsulfonamides: Combined Experimental and Computational Studies.
作者： Xujing Duan , Wei Yi , Xingwei Li , Guangfan Zheng , Zhi Zhou
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摘要: Cyclopropane rings are a prominent structural motif in biologically active molecules. Enantio- and diastereoselective construction of cyclopropanes through C-H activation arenes coupling with readily available cyclopropenes is highly appealing but remains challenge. A dual directing-group-assisted strategy was used to realize mild redox-neutral RhIII -catalyzed cyclopropylation N-phenoxylsulfonamides enantioselective, diastereoselective, regioselective fashion cyclopropenyl secondary alcohols as cyclopropylating reagent. Synthetic applications demonstrated highlight the potential developed method. Integrated experimental computational mechanistic studies revealed that reaction proceeds via RhV nitrenoid intermediate, Noyori-type outer sphere concerted proton-hydride transfer from alcohol Rh=N bond produces observed trans selectivity.
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