3307-19-5Relevant articles and documents
A Ball-Milling-Enabled Cross-Electrophile Coupling
Jones, Andrew C.,Nicholson, William I.,Leitch, Jamie A.,Browne, Duncan L.
supporting information, p. 6337 - 6341 (2021/08/23)
The nickel-catalyzed cross-electrophile coupling of aryl halides and alkyl halides enabled by ball-milling is herein described. Under a mechanochemical manifold, the reductive C-C bond formation was achieved in the absence of bulk solvent and air/moisture sensitive setups, in reaction times of 2 h. The mechanical action provided by ball milling permits the use of a range of zinc sources to turnover the nickel catalytic cycle, enabling the synthesis of 28 cross-electrophile coupled products.
Nickel-Catalyzed Cross-Electrophile Coupling of Aryl Chlorides with Primary Alkyl Chlorides
Gilbert, Michael M.,Goldfogel, Matthew J.,Kim, Seoyoung,Weix, Daniel J.
supporting information, p. 9902 - 9907 (2020/06/27)
Alkyl chlorides and aryl chlorides are among the most abundant and stable carbon electrophiles. Although their coupling with carbon nucleophiles is well developed, the cross-electrophile coupling of aryl chlorides with alkyl chlorides has remained a chall
Iron-catalyzed cross coupling of aryl chlorides with alkyl Grignard reagents: Synthetic scope and FeII/FeIV mechanism supported by x-ray absorption spectroscopy and density functional theory calculations
Agata, Ryosuke,Takaya, Hikaru,Matsuda, Hiroshi,Nakatani, Naoki,Takeuchi, Katsuhiko,Iwamoto, Takahiro,Hatakeyama, Takuji,Nakamura, Masaharu
supporting information, p. 381 - 390 (2019/02/25)
A combination of iron(III) fluoride and 1,3-bis(2,6-diiso-propylphenyl)imidazolin-2-ylidene (SIPr) catalyzes the high-yielding cross coupling of an electron-rich aryl chloride with an alkyl Grignard reagent, which cannot be attained using other iron catalysts. A variety of alkoxy-or amino-substituted aryl chlorides can be cross-coupled with various alkyl Grignard reagents regardless of the presence or absence of β-hydrogens in the alkyl group. A radical probe experiment using 1-(but-3-enyl)-2-chlorobenzene does not afford the corresponding cyclization product, therefore excluding the intermediacy of radical species. Solution-phase X-ray absorption spectroscopy (XAS) analysis, with the help of density functional theory (DFT) calculations, indicates the formation of a high-spin (S = 2) heteroleptic difluorido organoferrate(II), [MgX][FeIIF2(SIPr)-(Me/alkyl)], in the reaction mixture. DFT calculations also support a feasible reaction pathway, including the formation of a difluorido organoferrate(II) intermediate which undergoes a novel Lewis acid-assisted oxidative addition to form a neutral organoiron(IV) intermediate, which leads to an FeII/FeIV cata-lytic cycle, where the fluorido ligand and the magnesium ion play key roles.
