1717-84-6Relevant articles and documents
Iron-catalyzed coupling of aryl grignard reagents with alkyl halides: A competitive hammett study
Hedstroem, Anna,Bollmann, Ulla,Bravidor, Jenny,Norrby, Per-Ola
, p. 11991 - 11993 (2011)
Competing for electrophiles: The elusive iron-catalyzed C-C coupling reaction was investigated and analyzed by a Hammett study of the nucleophilic partner. This required finding conditions in which the iron catalyst is stable in the presence of an excess of the Grignard reagent. The selectivity- determining step seems to be the transmetalation, occurring either before or after the oxidative addition step (see scheme).
Cu-Catalyzed Generation of Alkyl Radicals from Alkylsilyl Peroxides and Subsequent C(sp3)-C(sp2) Cross-Coupling with Arylboronic Acids
Maruoka, Keiji,Sakamoto, Ryu,Sakurai, Shunya,Tsuzuki, Saori
, p. 3973 - 3980 (2020)
This work describes a novel and practical method for the Cu-catalyzed C(sp3)-C(sp2) cross-coupling of alkylsilyl peroxides with arylboronic acids. The reductive cleavage of the O-O bond of alkylsilyl peroxides and the desired cross-coupling reactions to afford alkyl-substituted aromatic rings proceed smoothly at room temperature promoted by simple Cu-based catalysts and do not require activation by visible light. The results of mechanistic investigations support a radical-mediated C(sp3)-C(sp2) bond formation via β-scission of the alkoxy radicals generated from the alkylsilyl peroxides.
Cross-Coupling Reactions of Alkyl Halides with Aryl Grignard Reagents Using a Tetrachloroferrate with an Innocent Countercation
Hashimoto, Toru,Maruyama, Tsubasa,Yamaguchi, Takamichi,Matsubara, Yutaka,Yamaguchi, Yoshitaka
supporting information, p. 4232 - 4236 (2019/08/16)
Bis(triphenylphosphoranylidene)ammonium tetrachloroferrate, (PPN)[FeCl4] (1), was evaluated as a catalyst for cross-coupling reactions. 1 exhibits high stability toward air and moisture and is an effective catalyst for the reaction of secondary alkyl halides with aryl Grignard reagents. The PPN cation is considered as an innocent counterpart to the iron center. We have developed an easy-to-handle iron catalyst for “ligand-free” cross-coupling reactions. (Figure presented.).
Nickel-catalyzed selective oxidative radical cross-coupling: An effective strategy for inert Csp3-H functionalization
Liu, Dong,Li, Yuxiu,Liu, Chao,Lei, Aiwen,Qi, Xiaotian,Lan, Yu.
supporting information, p. 998 - 1001 (2015/03/30)
An effective strategy for inert Csp3-H functionalization through nickel-catalyzed selective radical cross-couplings was demonstrated. Density functional theory calculations were conducted and strongly supported the radical cross-coupling pathway assisted by nickel catalyst, which was further confirmed by radical-trapping experiments. Different arylborates including arylboronic acids, arylboronic acid esters and 2,4,6-triarylboroxin were all good coupling partners, generating the corresponding Csp3-H arylation products in good yields.
Efficient cross-coupling of aryl Grignard reagents with alkyl halides by recyclable ionic iron(iii) complexes bearing a bis(phenol)-functionalized benzimidazolium cation
Xia, Chong-Liang,Xie, Cun-Fei,Wu, Yu-Feng,Sun, Hong-Mei,Shen, Qi,Zhang, Yong
, p. 8135 - 8144 (2013/12/04)
A novel bis(phenol)-functionalized benzimidazolium salt, 1,3-bis(3,5-di-tert-butyl-2-hydroxybenzyl)benzimidazolium chloride (H 3LCl, 1), was designed and used to prepare ionic iron(iii) complexes of the type [H3L][FeX4] (X = Cl, 2; X = Br, 3). Both 2 and 3 were characterized by elemental analysis, Raman spectroscopy, electrospray ionization mass spectrometry and X-ray crystallography. The catalytic performances of 2 and 3 in cross-coupling reactions using aryl Grignard reagents with primary and secondary alkyl halides bearing β-hydrogens were studied. This analysis shows that complex 2 has good potential for alkyl chloride-mediated coupling. In comparison, complex 3 showed slightly lower catalytic activity. After decanting the product contained in the ethereal layer, complex 2 could be recycled at least eight times without significant loss of catalytic activity.
IRON BISPHENOLATE COMPLEXES AND METHODS OF USE AND SYNTHESIS THEREOF
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Paragraph 00187-00191, (2013/04/25)
The present application, relates to iron bisphenolate complexes and methods of use and synthesis thereof. The iron complexes are prepared from tridentate or tetradentate ligands of Formula I: wherein R1 and R2 are as defined herein. Also provided are methods and processes of using the iron bisphenolate complexes as catalysts in cross-coupling reactions and in controlled radical polymerizations.
A comprehensive study of the effects of spectator ligands, transition metals and lithium halide additives on the efficiency of iron, nickel and palladium-catalyzed cross-coupling reactions of cyclohexyl magnesium bromide with fluorinated bromobenzenes
Dahadha, Adnan,Imhof, Wolfgang
, p. 200 - 216 (2013/10/21)
Thirteen mono-, bis- and trifluorinated bromobenzene derivatives have been coupled with cyclohexyl magnesium bromide or the corresponding lithiumchloride or lithiumbromide adducts. Iron, nickel and palladium complexes of the general formula [MCl2(dppx)] (x = (CH2)n, n = 1, 2, 3) have been used as the precatalysts. Palladium based catalysts give high yields of the coupling product with the Grignard reagent itself whereas lithium halides are needed as additives to achieve comparable efficiencies if nickel and iron catalysts are used. Yields also depend on the chain length of the bridging units and on the fact whether fluorine substituents are present in ortho position with respect to bromine.
Cross-coupling of non-activated chloroalkanes with aryl grignard reagents in the presence of iron/N-heterocyclic carbene catalysts
Ghorai, Sujit K.,Jin, Masayoshi,Hatakeyama, Takuji,Nakamura, Masaharu
supporting information; experimental part, p. 1066 - 1069 (2012/04/10)
An efficient and high-yielding cross-coupling reaction of various primary, secondary, and tertiary alkyl chlorides with aryl Grignard reagents was achieved by using catalytic amounts of N-heterocyclic carbene ligands and iron salts. This reaction is a simple and efficient arylation method having applicability to a wide range of industrially abundant chloroalkanes, including polychloroalkanes, which are challenging substrates under conventional cross-coupling conditions.
Ionic iron(iii) complexes of bis(phenol)-functionalized imidazolium cations: Synthesis, structures and catalysis for aryl Grignard cross-coupling of alkyl halides
Deng, Hai-Ning,Xing, Ya-Lin,Xia, Cong-Liang,Sun, Hong-Mei,Shen, Qi,Zhang, Yong
, p. 11597 - 11607 (2013/02/23)
A series of bis(phenol)-functionalized imidazolium salts, 1,3-bis(4,6-di-R1-2-hydroxybenzyl)-2-R2-4,5-di-R 3-imidazolium chlorides H3LnCl (R1 = tBu, R2 = R3 = H, H3L 1Cl, 1; R1 = CH3, R2 = R3 = H, H3L2Cl, 2; R1 = tBu, R 2 = H, R3 = Cl, H3L3Cl, 3; R 1 = tBu, R2 = CH3, R3 = H, H3L4Cl, 4), were used to produce a novel series of ionic iron(iii) complexes [H3Ln][FeX4] (n = 1, X = Cl, 5; n = 2, X = Cl, 6; n = 3, X = Cl, 7; n = 4, X = Cl, 8; n = 1, X = Br, 9; n = 3, X = Br, 10). All of the complexes were characterized by Raman spectroscopy and electrospray ionization mass spectrometry. Elemental analysis and X-ray crystallography were also used. All of the complexes were non-hygroscopic and air-stable, with five of them existing as solids (5, 7-10) and one as an oil (6) at room temperature. A preliminary catalytic study on the cross-coupling reactions of aryl Grignard reagents with primary and secondary alkyl halides bearing β-hydrogens, revealed that all of the ionic iron(iii) complexes exhibited good to excellent catalytic activity. Complexes 5, 6 and 8 exhibited optimal activity, whereas 7, 9 and 10 showed only moderate activity. Furthermore, by simply decanting the cross-coupling product in the ether layer, complexes 5 and 6 could be reused in at least seven successive runs without significant loss in catalytic activity.
Synthesis of iron(III) complex bearing tridentate β-Aminoketonato Ligand: Application to iron-catalyzed cross-coupling reaction of arylmagnesium bromides with alkyl halides
Yamaguchi, Yoshitaka,Ando, Hiroaki,Nagaya, Makoto,Hinago, Hideto,Ito, Takashi,Asami, Masatoshi
supporting information; experimental part, p. 983 - 985 (2011/12/05)
A tridentate β-aminoketonato iron complex was prepared by the reaction of lithium β-aminoketonato with FeCl3. This iron complex was found to be an efficient catalyst for the crosscoupling reaction between arylmagnesium bromides and alkyl halides.
