- Bulky Diamine Ligand Promotes Cross-Coupling of Difluoroalkyl Bromides by Iron Catalysis
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Although iron-catalyzed cross-coupling of Grignard reagents with alkyl halides has been well established, the adoption of the reaction for fluoroalkylations has not been reported because traditional catalytic systems often lead to defluorination reactions. Described herein is the investigation of an iron-catalyzed cross-coupling between arylmagnesium bromides and difluoroalkyl bromides with modified N,N,N′,N′-tetramethyl-ethane-1,2-diamine (TMEDA) as a ligand. The use of this bulky diamine, in which a butylene is substituted at one carbon atom of the ethylene backbone in TMEDA, enables the iron-catalyzed difluoroalkylation under mild reaction conditions with a wide range of difluoroalkyl bromides, including vulnerable bromodifluoromethane, thus providing a general and cost-efficient route for applications in medicinal chemistry.
- An, Lun,Xiao, Yu-Lan,Zhang, Shu,Zhang, Xingang
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supporting information
p. 6921 - 6925
(2018/05/07)
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- THE REACTIONS OF N,N-DIMETHYLPHOSPHORAMIDIC DIFLUORIDE WITH TRANS-2-SUBSTITUTED CYCLOALKANOLS
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An interaction between N,N-dimethylphosphoramidic difluoride and cyclic alcohols containing hydroxyl, alkylamine and methylthiol groups in the trans-β-position was performed. Trans-1-ethylcyclopentane-1,2-diol and trans-2-(N-alkylamino)cyclopentanols react with N,N-dimethylphosphoramidic difluoride to yield 1-ethyl-6-oxabicyclo(3.1.0)hexane and 6-alkyl-6-azabicyclo(3.1.0)hexane, respectively. In the case of trans-2-(N,N-dialkylamino)cyclopentanols and cyclohexanols, such reaction gives a salt of phosphorodifluoridic acid and the corresponding cyclic N,N,N',N'-tetraalkyl-1,2-diamine whereas trans-2-methylthiocyclopentanol is converted to a salt of phosphorodifluoridic acid and N,N-dimethyl-N-(2-methylthiocyclopentyl)amine. Some of described reactions appear to be applicable for the synthesis of various organic compounds, e.g. phosphorylated 2-N,N-dialkylaminocyclopentanethiols. Key words: N,N-dimethylphosphoramidic difluoride, N,N-dimethylphosphoramidothioic difluoride, phosphorodifluoridic acid, phosphorylated dialkylaminocyclopentanethiol, N,N-dialkylaminocycloalkanol, N,N,N',N'-tetraalkyl-1,2-diamine.
- Fokin, E. A.,Sadovnikov, S. V.,Sosnov, A. V.
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