569-72-2Relevant articles and documents
Dehalogenative Cross-Coupling of gem-Difluoroalkenes with Alkyl Halides via a Silyl Radical-Mediated Process
Tian, Hao,Yang, Shaoxiang,Wang, Xiaochen,Xu, Wentao,Liu, Yuxiu,Li, Yongqiang,Wang, Qingmin
, p. 12772 - 12782 (2021/09/13)
Herein, we describe a convenient general protocol for monofluoroalkenylation reactions of alkyl bromides involving cooperative visible-light photoredox catalysis and halogen abstraction. Mechanistic experiments showed that the products were generated by selective cross-coupling of aliphatic radicals with fluoroalkenyl radicals. Silyl radical-mediated halogen abstraction enabled the protocol to be used for the monofluoroalkenylation of a broad range of alkyl and heteroaryl halides. The protocol could be carried out on a gram scale and was applied to cholesterol, indicating its utility for late-stage monofluoroalkenylation reactions.
Visible-light-promotedE-selective synthesis of α-fluoro-β-arylalkenyl sulfidesviathe deoxygenation/isomerization process
Li, Yuxiu,Li, Xiangqian,Li, Xiaowei,Shi, Dayong
supporting information, p. 2152 - 2155 (2021/03/06)
Regioselective synthesis of α-fluoro-β-arylalkenyl sulfides has been established withgem-difluoroalkenes and sodium sulfinates in a transition-metal-free manner. A series of control experiments were executed to demonstrate thiol radicals and anions as the proposed intermediates. Notably, regioselectiveZ→Eisomerization was achieved under green light irradiation in the absence of a photoinitiator.
From C1 to C3: Copper-Catalyzed gem-Bis(trifluoromethyl)olefination of α-Diazo Esters with TMSCF3
Hu, Jinbo,Hu, Mingyou,Liu, Qinghe,Ni, Chuanfa,Pan, Shitao,Wang, Qian,Xie, Qiqiang
, p. 8507 - 8511 (2020/04/15)
A Cu-catalyzed gem-bis(trifluoromethyl)olefination of α-diazo esters, using TMSCF3 as the only fluorocarbon source, has been developed and provides an exquisite method to access gem-bis(trifluoromethyl)alkenes. This unprecedented olefination pr
Organocatalytic Nucleophilic Substitution Reaction of gem-Difluoroalkenes with Ketene Silyl Acetals
Kondoh, Azusa,Koda, Kazumi,Terada, Masahiro
, p. 2277 - 2280 (2019/03/26)
An organocatalytic nucleophilic substitution reaction of gem-difluoroalkenes with ketene silyl acetals was developed. Phosphazene P4-tBu effectively catalyzed the reaction under mild conditions to provide monofluoroalkenes possessing an alkoxycarbonylmethyl group in high yields with high Z selectivities.
Direct α-Monofluoroalkenylation of Heteroatomic Alkanes via a Combination of Photoredox Catalysis and Hydrogen-Atom-Transfer Catalysis
Tian, Hao,Xia, Qing,Wang, Qiang,Dong, Jianyang,Liu, Yuxiu,Wang, Qingmin
, p. 4585 - 4589 (2019/06/17)
In this study, a new C(sp3)-H monofluoroalkenylation reaction involving cooperative visible-light photoredox catalysis and hydrogen-atom-transfer catalysis to afford products generated by selective hydrogen abstraction and radical-radical cross-coupling was described. This mild, efficient reaction shows high regioselectivity for the α-carbon atoms of amines, ethers, and thioethers and thus allows the preparation of monofluoroalkenes bearing various substituents. The reaction was applied to two bioactive molecules, indicating its utility for late-stage monofluoroalkenylation of compounds with inert C(sp3)-H bonds.
Trifluoromethylation and Monofluoroalkenylation of Alkenes through Radical–Radical Cross-Coupling
Wang, Qiang,Qu, Yi,Tian, Hao,Liu, Yuxiu,Song, Hongjian,Wang, Qingmin
, p. 8686 - 8690 (2019/06/17)
The first visible-light-induced trifluoromethylation and monofluoroalkenylation of simple alkenes via a challenging radical–radical cross-coupling step was achieved. This method provided a mild, step-economical and redox-neutral route to privileged two different fluorinated difunctionalized allyl compounds. The utility of this method is illustrated by late-stage modification of medically important molecules.
Nucleophilic difluoromethylation of aromatic aldehydes using trimethyl(trifluoromethyl)silane (TMSCF3)
Krishnamoorthy, Sankarganesh,Kar, Sayan,Kothandaraman, Jotheeswari,Prakash, G.K. Surya
, p. 10 - 14 (2018/02/14)
Reaction of the Ruppert–Prakash reagent (Me3SiCF3) with aromatic aldehydes in the presence of triphenylphosphine, lithium iodide and lithium tetrafluoroborate selectively furnishes gem-difluorinated phosphonium salts. Simple alkaline
Synthesis of 2,2-diaryl-1,1-difluoroethenes via Pd-catalyzed dehydrosulfonylative cross-coupling of α-[difluoro(phenylsulfonyl)methyl]benzyl tosylates with arylboronic acids
Zhang, Rui,Ni, Chuanfa,Zhao, Yanchuan,Hu, Jinbo
, p. 5295 - 5302 (2018/05/16)
By using PhSO2CF2H as the difluoromethylidene equivalent, a novel method for connecting aromatic aldehydes and arylboronic acids via consecutive reactions was developed to obtain structurally diverse 2,2-diaryl-1,1-difluoroethenes. The key step is the palladium-catalyzed dehydrosulfonylative cross-coupling of tosylates that are prepared from PhSO2CF2H, aromatic aldehydes and tosyl chloride. Mechanistic investigations showed that the reaction proceeds mainly through base-mediated dehydrosulfonylation followed by palladium-catalyzed C(sp2)-C(sp2) cross-coupling reaction.
Palladium-Catalyzed Fluoroarylation of gem-Difluoroalkenes
Tang, Hai-Jun,Lin, Ling-Zhi,Feng, Chao,Loh, Teck-Peng
, p. 9872 - 9876 (2017/08/08)
A Pd-catalyzed fluoroarylation of gem-difluoroalkenes with aryl halides is reported. By taking advantage of the in situ generated α-CF3-benzylsilver intermediates derived from the nucleophilic addition of silver fluoride to gem-difluoroalkenes, this strategy bypasses the use of a strong base, thus enabling a mild and general synthetic method for ready access to non-symmetric α,α-disubstituted trifluoroethane derivatives.
Visible light photocatalytic decarboxylative monofluoroalkenylation of α-amino acids with: Gem -difluoroalkenes
Li, Jingjing,Lefebvre, Quentin,Yang, Haijun,Zhao, Yufen,Fu, Hua
, p. 10299 - 10302 (2017/09/25)
α-Amino acids are among the most common biologically active molecules in nature, and their functionalization has attracted much attention. In this communication, a novel, efficient and general visible-light photocatalytic decarboxylative monofluoroalkenylation of N-protected α-amino acids with gem-difluoroalkenes is reported, affording the corresponding α-amino monofluoroalkenes which might find applications in medical chemistry and materials science. The reaction proceeded at room temperature with high efficiency and tolerance of various functional groups.
