- Palladium-catalyzed allylic alkylation dearomatization of β-naphthols and indoles withgem-difluorinated cyclopropanes
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A palladium-catalyzed allylic alkylation dearomatization of β-naphthols and indoles withgem-difluorinated cyclopropanes has been developed. This reaction provided an efficient route to access 2-fluoroallylic β-naphthalenones and indolenines bearing quaternary carbon centers in good yields with highZ-selectivityviaC-C bond activation, C-F bond cleavage and the dearomatization process, benefiting from the wide substrate scope and good functional group tolerance. Moreover, 2-fluoroallylic furanoindoline and pyrroloindolines were achieved in good efficiencyviacascade allylic alkylation, dearomatization and cyclization processes in the presence of Et3B.
- Fu, Zhiyuan,Zhu, Jianping,Guo, Songjin,Lin, Aijun
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supporting information
p. 1262 - 1265
(2021/02/09)
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- Rhodium Catalyzed Regioselective C?H Allylation of Simple Arenes via C?C Bond Activation of Gem-difluorinated Cyclopropanes
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Herein, we report a rhodium catalyzed directing-group free regioselective C?H allylation of simple arenes. Readily available gem-difluorinated cyclopropanes can be employed as highly reactive allyl surrogates via a sequence of C?C and C?F bond activation, providing allyl arene derivatives in good yields with high regioselectivity under mild conditions. The robust methodology enables facile late-stage functionalization of complex bioactive molecules. The high efficiency of this reaction is also demonstrated by the high turnover number (TON, up to 1700) of the rhodium catalyst on gram-scale experiments. Preliminary success on kinetic resolution of this transformation is achieved, providing a promising access to enantio-enriched gem-difluorinated cyclopropanes.
- Jiang, Zhong-Tao,Huang, Jiangkun,Zeng, Yaxin,Hu, Fangdong,Xia, Ying
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supporting information
p. 10626 - 10631
(2021/04/05)
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- Palladium-Catalyzed Defluorinative Alkylation of gem-Difluorocyclopropanes: Switching Regioselectivity via Simple Hydrazones
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Conventional approaches for Pd-catalyzed ring-opening cross-couplings of gem-difluorocyclopropanes with nucleophiles predominantly deliver the β-fluoroalkene scaffolds (linear selectivity). Herein, we report a cooperative strategy that can completely switch the reaction selectivity to give the alkylated α-fluoroalkene skeletons (branched selectivity). The unique reactivity of hydrazones that enables analogous inner-sphere 3,3′-reductive elimination driven by denitrogenation, as well as the assistance of steric-embedded N-heterocyclic carbene ligand, are the key to switch the regioselectivity. A wide range of hydrazones derived from naturally abundant aryl and alkyl aldehydes are well applicable, and various gem-difluorocyclopropanes, including modified pharmaceutical and biological molecules, can be efficiently functionalized with high value alkylated α-fluorinated alkene motifs under mild conditions.
- Lv, Leiyang,Li, Chao-Jun
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supporting information
p. 13098 - 13104
(2021/05/03)
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- Palladium-Catalyzed Ring-Opening Coupling of gem-Difluorocyclopropanes for the Construction of 2-Fluoroallylic Sulfones
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A Pd-catalyzed ring-opening sulfonylation of gem-difluorocyclopropanes is reported. This protocol involves C-C bond cleavage, β-F elimination, and allylic coupling to form corresponding 2-fluoroallylic sulfones efficiently with Z-selectivity. Different substrates bearing diverse functional groups are tolerated. Moreover, this method is successfully used for the late-stage derivation of several bioactive molecules.
- Ni, Jiabin,Nishonov, Bekzod,Pardaev, Azizbek,Zhang, Ao
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p. 13646 - 13654
(2019/11/11)
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- Model II fluorine asia [...] inner salt synthesis and its application
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The present invention provides synthesis and application of difluoro methylene phosphorus inner salt, wherein the compound has a structure shown in Formula A: (R1R2R3)P+CF2CO2 -. The definitions of substituent groups are described in the specification. Th
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Paragraph 0270-0272
(2018/01/11)
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