Main observation and conclusion Alkoxy radical-mediated carbon-carbon bond cleavages have emerged as a powerful strategy to complement traditional ionic-type transformations.However,carbon-carbon cleavage reaction tri...Main observation and conclusion Alkoxy radical-mediated carbon-carbon bond cleavages have emerged as a powerful strategy to complement traditional ionic-type transformations.However,carbon-carbon cleavage reaction triggered by alkoxy radical intermediate derived from the combination of alkyl radical and dioxygen,is scarce and underdeveloped.Herein,we report alkoxy radical,which was generated from alkyl radical and dioxygen,mediated selective cleavage of unstrained carbon-carbon bond for the oxysulfonylation of 1,1-disubstituted alkenes,providing facile access to a variety of valuableβ-keto sulfones.Mechanistic experiments indicated alkoxy radical intermediate that underwent subsequent regioselectiveβ-scission might be involved in the reaction and preliminary computational studies were conducted to provide a detailed explanation on the regioselectivity of the C-C bond cleavage.Notably,the strategy was successfully applied for constructing uneasily obtained architecturally intriguing molecules.展开更多
Symmetrical diynes were synthesized by ligand-free copper-catalyzed homocoupling reaction of 1,1-dibromo-1- alkenes using a DBU/DMSO system at room temperature in good to excellent yields.
Many of the commonly used pharmaceuticals and biologically active natural products are nitrogencontaining compounds.Recently,the transitionmetal-catalyzed or the radical-mediated 1,2-carboamination of alkenes has been...Many of the commonly used pharmaceuticals and biologically active natural products are nitrogencontaining compounds.Recently,the transitionmetal-catalyzed or the radical-mediated 1,2-carboamination of alkenes has been well explored to access amine scaffolds.However,synthetic strategies toward the 1,1-carboamination of alkenes are severely limited.Herein,we describe a method to achieve the 1,1-arylamination using readily available building blocks enabled by palladium catalysis.This sequential three step-Heck arylation,metal migration,followed by aza-1,6-Micheal addition process exhibits excellent chemo-and regioselectivity.To showcase the potential as a method for diversity-oriented drug discovery,the modification of numerous structurally complex bioactive molecules was also successfully performed.展开更多
基金Fund of Luzhou Government and Southwest Medical University(Nos.2019LZXNYDJ28,2018LZXNYD-ZK33,2018LZXNYD-ZK39)the Open Project of Central Nervous System Drug Key Laboratory of Sichuan Province(No.200023-01SZ)the research fund of Southwest Medical University(Nos.2017-ZRZD-020 and 2017-ZRQN-031).
文摘Main observation and conclusion Alkoxy radical-mediated carbon-carbon bond cleavages have emerged as a powerful strategy to complement traditional ionic-type transformations.However,carbon-carbon cleavage reaction triggered by alkoxy radical intermediate derived from the combination of alkyl radical and dioxygen,is scarce and underdeveloped.Herein,we report alkoxy radical,which was generated from alkyl radical and dioxygen,mediated selective cleavage of unstrained carbon-carbon bond for the oxysulfonylation of 1,1-disubstituted alkenes,providing facile access to a variety of valuableβ-keto sulfones.Mechanistic experiments indicated alkoxy radical intermediate that underwent subsequent regioselectiveβ-scission might be involved in the reaction and preliminary computational studies were conducted to provide a detailed explanation on the regioselectivity of the C-C bond cleavage.Notably,the strategy was successfully applied for constructing uneasily obtained architecturally intriguing molecules.
基金Project supported by the National Natural Science Foundation of China （No. 30873153）, and the Key Projects of Shanghai in Biomedical （No. 08431902700）.
文摘Symmetrical diynes were synthesized by ligand-free copper-catalyzed homocoupling reaction of 1,1-dibromo-1- alkenes using a DBU/DMSO system at room temperature in good to excellent yields.
基金supported by the National Science Foundation of China(no.22071267)the National Science and Technology Major Project“Key New Drug Creation and Manufacturing Program,”China(no.2020ZX09201015)+1 种基金the Innovation Team of the“DoubleFirst Class Initiative”(nos.CPU2018GY04 and CPU2018GY35)the Foundation of the Open Project of State Key Laboratory of Natural Medicines(no.SKLNMZZ202023).
文摘Many of the commonly used pharmaceuticals and biologically active natural products are nitrogencontaining compounds.Recently,the transitionmetal-catalyzed or the radical-mediated 1,2-carboamination of alkenes has been well explored to access amine scaffolds.However,synthetic strategies toward the 1,1-carboamination of alkenes are severely limited.Herein,we describe a method to achieve the 1,1-arylamination using readily available building blocks enabled by palladium catalysis.This sequential three step-Heck arylation,metal migration,followed by aza-1,6-Micheal addition process exhibits excellent chemo-and regioselectivity.To showcase the potential as a method for diversity-oriented drug discovery,the modification of numerous structurally complex bioactive molecules was also successfully performed.
