1680-58-6

The homocoupling of aryl halides and the heterocoupling of aryl halides with either aryl bromides or arenes bearing an ortho-lithiation directing group are presented. The use of a Pd catalyst, in combination with t-BuLi, allows for the rapid and efficient formation of a wide range of polyaromatic compounds in a one pot procedure bypassing the need for the separate preformation of an organometallic coupling partner. These polyaromatic structures are obtained in high yields, in 10 min at room temperature, with minimal waste generation (E-factors as low as 1.5) and without the need for strict inert conditions, making this process highly efficient and practical in comparison to classical methods. As illustration, several key intermediates of widely used BINOL-derived structures are readily prepared.

A series of ionic iron(III) complexes of general formula [HLn][FeX4] (HL1?=?1,3-dibenzylbenzimidazolium cation, X?=?Cl, 1; HL1, X?=?Br, 2; HL2?=?1,3-dibutylbenzimidazolium cation, X?=?Br, 3; HL3?=?1,3-bis(diphenylmethyl)benzimidazolium cation, X?=?Br, 4) were easily prepared in high yields by the direct reaction of FeX3 with 1 equiv. of [HLn]X under mild conditions. All of them were characterized using elemental analysis, Raman spectroscopy and electrospray ionization mass spectrometry, and X-ray crystallography for 1 and 4. In the presence of magnesium turnings and LiCl, these air- and moisture-insensitive complexes showed high catalytic activities in direct cross-couplings of aryl phosphates with primary and secondary alkyl bromides with broad substrate scope, wherein complex 4 was the most effective.

A novel family of ionic iron(ii) complexes of the general formula [HL][Fe(PR′3)X3] (HL = 1,3-bis(2,6-diisopropylphenyl)imidazolium cation, HIPr, R′ = Ph, X = Cl, 2; HL = HIPr, R′ = Cy, X = Cl, 3; HL = HIPr, R′ = Ph, X = Br, 4; HL = HIPr, R′ = Cy, X = Br, 5; HL = 1,3-bis(2,4,6-trimethylphenyl)imidazolium cation, HIMes, R′ = Cy, X = Br, 6) was easily prepared via a stepwise approach in 88%-92% yields. In addition, an ionic iron(ii) complex, [HIPr][Fe(C4H8O)Cl3] (1), has been isolated from the reaction of FeCl2(THF)1.5 with one equiv. of [HIPr]Cl in 90% yield and it can further react with one equiv. of PPh3 or PCy3, affording the corresponding target iron(ii) complex 2 or 3, respectively. All these complexes were characterized by elemental analysis, electrospray ionization mass spectrometry (ESI-MS), 1H NMR spectroscopy and X-ray crystallography. These air-insensitive complexes 2-6 showed high catalytic activities in the cross-coupling of aryl phosphates with primary and secondary alkyl Grignard reagents with a broad substrate scope, wherein [HIPr][Fe(PCy3)Br3] (5) was the most effective. Complex 5 also catalyzes the reductive cross-coupling of aryl phosphates with unactivated alkyl bromides in the presence of magnesium turnings and LiCl, as well as the corresponding one-pot acylation/cross-coupling sequence under mild conditions.

An operationally simple cross-coupling reaction between aryl halides and alkyl halides with high selectivity has been developed. The underlying domino process utilizes CoCl2/Me4-DACH as a catalyst system. The methodology exhibits hig

A process for producing alkylnaphthalenes by alkylating naphthalene with an olefin having 2 to 4 carbon atoms, which comprises (1) introducing the olefin into a solution of crude naphthalene containing thianaphthene as an impurity in a solvent having a boiling point sufficiently different from the boiling point of the naphthalene and alkylnaphthalenes produced that the solvent is separable by distillation in the presence of (i) an aluminum chloride complex consisting of (a) aluminum chloride, (b) hydrogen chloride and (c) an alkylated benzene or naphthalene, or (ii) a solid aluminum chloride which is dissolved into the reaction solution by adding gaseous hydrogen chloride simultaneously with or prior to the introducing of the olefin, (2) aging the reaction solution, and (3) recovering the resulting alkylnaphthalenes, whereby alkylnaphthalenes, containing as monoalkylnaphthalenes a predominant amount of a β-monoalkylnaphthalene, are obtained in a high yield.