- Iron-Catalyzed Tertiary Alkylation of Terminal Alkynes with 1,3-Diesters via a Functionalized Alkyl Radical
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Direct oxidative C(sp)?H/C(sp3)?H cross-coupling offers an ideal and environmentally benign protocol for C(sp)?C(sp3) bond formations. As such, reactivity and site-selectivity with respect to C(sp3)?H bond cleavage have remained a persistent challenge. Herein is reported a simple method for iron-catalyzed/silver-mediated tertiary alkylation of terminal alkynes with readily available and versatile 1,3-dicarbonyl compounds. The reaction is suitable for an array of substrates and proceeds in a highly selective manner even employing alkanes containing other tertiary, benzylic, and C(sp3)?H bonds alpha to heteroatoms. Elaboration of the products enables the synthesis of a series of versatile building blocks. Control experiments implicate the in situ generation of a tertiary carbon-centered radical species.
- Tian, Ming-Qing,Shen, Zhen-Yao,Zhao, Xuefei,Walsh, Patrick J.,Hu, Xu-Hong
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supporting information
p. 9706 - 9711
(2021/03/19)
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- Selective Alkenylation and Hydroalkenylation of Enol Phosphates through Direct C-H Functionalization
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An efficient and selective Rh-catalyzed direct C-H functionalization reaction of enol phosphates was developed. The method is applicable to a variety of coupling partners, including activated alkenes, alkynes, and allenes, and leads to the formation of various valuable alkenylated and hydroalkenylated enol phosphates through the action of the phosphate directing group. The versatility and utility of the coupling products were demonstrated through further transformations into synthetically useful building blocks. P points the way: A direct C-H functionalization of enol phosphates was developed. The method is applicable to a variety of coupling partners, including activated alkenes, alkynes, and allenes, and it leads to the formation of alkenylated and hydroalkenylated enol phosphates through the action of the phosphate directing group. The utility of the coupling products are demonstrated by further transformations into synthetically useful building blocks.
- Hu, Xu-Hong,Yang, Xiao-Fei,Loh, Teck-Peng
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supporting information
p. 15535 - 15539
(2016/01/26)
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