79835-99-7

Upstream product

• 107514-36-3 (R)-1-Methyl-2-oct-1-enylidene-cyclohexane 
• 107514-36-3 (S)-1-Methyl-2-oct-1-enylidene-cyclohexane 
• 18409-17-1 (E)-oct-2-en-1-ol 
• 108-88-3 toluene 
• 3391-86-4 1-octen-3-ol 
• 932-31-0 ortho-tolylmagnesium bromide 
• 111-83-1 1-bromo-octane 
• 629-27-6 1-Iodooctane 
• 95-46-5 2-methylphenyl bromide 
• 463-11-6 1-Fluoro-octane 
• 106-99-0 buta-1,3-diene 
• 16156-52-8 n-octyl methanesulfonate 
• 38841-98-4 n-octylmagnesium chloride 

Relevant academic research and scientific papers

A Ball-Milling-Enabled Cross-Electrophile Coupling

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 coupling reaction of alkyl halides with aryl Grignard reagents in the presence of 1,3-butadiene: Mechanistic studies of four-component coupling and competing cross-coupling reactions

We describe the mechanism, substituent effects, and origins of the selectivity of the nickel-catalyzed four-component coupling reactions of alkyl fluorides, aryl Grignard reagents, and two molecules of 1,3-butadiene that affords a 1,6-octadiene carbon framework bearing alkyl and aryl groups at the 3- and 8-positions, respectively, and the competing cross-coupling reaction. Both the four-component coupling reaction and the cross-coupling reaction are triggered by the formation of anionic nickel complexes, which are generated by the oxidative dimerization of two molecules of 1,3-butadiene on Ni(0) and the subsequent complexation with the aryl Grignard reagents. The C-C bond formation of the alkyl fluorides with the γ-carbon of the anionic nickel complexes leads to the four-component coupling product, whereas the cross-coupling product is yielded via nucleophilic attack of the Ni center toward the alkyl fluorides. These steps are found to be the rate-determining and selectivity-determining steps of the whole catalytic cycle, in which the C-F bond of the alkyl fluorides is activated by the Mg cation rather than a Li or Zn cation. ortho-Substituents of the aryl Grignard reagents suppressed the cross-coupling reaction leading to the selective formation of the four-component products. Such steric effects of the ortho-substituents were clearly demonstrated by crystal structure characterizations of ate complexes and DFT calculations. The electronic effects of the para-substituent of the aryl Grignard reagents on both the selectivity and reaction rates are thoroughly discussed. The present mechanistic study offers new insight into anionic complexes, which are proposed as the key intermediates in catalytic transformations even though detailed mechanisms are not established in many cases, and demonstrates their synthetic utility as promising intermediates for C-C bond forming reactions, providing useful information for developing efficient and straightforward multicomponent reactions.

IRON BISPHENOLATE COMPLEXES AND METHODS OF USE AND SYNTHESIS THEREOF

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.

Dinuclear iron complex-catalyzed cross-coupling of primary alkyl fluorides with aryl grignard reagents

Iron-catalyzed cross-coupling of nonactivated primary alkyl fluorides with aryl Grignard reagents has been achieved by using the low-coordinate dinuclear iron complex [(IPr2Me2)Fe(μ2-NDipp) 2Fe(IPr2Me2)] as the catalyst. This iron-catalyzed C(sp3)-F bond arylation reaction is applicable to a variety of aryl Grignard reagents and primary alkyl fluorides. The product pattern suggests the involvement of a radical-type mechanism for its C-F bond scission step.

Catalytic alkylation of aryl Grignard reagents by iron(iii) amine-bis(phenolate) complexes

Reaction of n-propylamino-N,N-bis(2-methylene-4-tert-butyl-6-methylphenol), H2L1, n-propylamino-N,N-bis(2-methylene-4,6-di-tert-butylphenol), H2L2, and benzylamino-N,N-bis(2-methylene-4-tert-butyl-6- methylphenol), H2L3, with anhydrous ferric chloride in the presence of base yields the products, [FeL1(μ-Cl)]2 (1), [FeL2(μ-Cl)]2 (2) and [FeL3(μ-Cl)]2 (3). In the solid state, these complexes exist as chloride-bridged dimers giving distorted trigonal bipyramidal iron(iii) ions. Reaction of H2L1 with FeBr 3, however, results in the formation of a tetrahedral iron(iii) complex possessing two bromide ligands. The amine-bis(phenolate) ligand is bidentate in this complex and bonds to the iron(iii) ion via the phenolate O-donors. The central amine donor is protonated, resulting in a quaternized ammonium fragment and the iron(iii) centre possesses a negative formal charge. As a result, this complex is zwitterionic and formulated as FeBr2L1H (4). Complex 1 is an air-stable, non-hygroscopic, single-component catalyst for C-C cross-coupling of aryl Grignard reagents with primary and secondary alkyl halides, including chlorides. Good to excellent yields of cross-coupled products are obtained in diethyl ether at room temperature. In some cases where low yields are obtained under these conditions, the use of microwave-assisted heating of the reaction mixture can improve yields. The Royal Society of Chemistry 2011.

Nickel-catalyzed reductive cross-coupling of aryl halides with alkyl halides

(Chemical Equation Presented) The direct reductive cross-coupling of alkyl halides with aryl halides is described. The transformation is efficient (equimolar amounts of the starting materials are used), generally high-yielding (all but one between 55 and 88% yield), highly functional-group-tolerant [OH, NHBoc, NHCbz, Bpin, C(O)Me, CO2Et, and CN are all tolerated], and easy to perform (uses only benchtop-stable reagents, tolerates small amounts of water and oxygen, changes color when complete, and uses filtration workup). The reaction appears to avoid the formation of intermediate organomanganese species, and a synergistic effect was found when a mixture of two ligands was employed.

Cobalt-catalyzed cross-coupling reactions of aryl bromides with alkyl grignard reagents

Aryl bromides react with primary alkyl Grignard reagents in the presence of N,N,N′,N′-tetramethyl-1,3-propanediamine and catalytic amounts of cobalt(II) chloride and an N-heterocyclic carbene to yield the corresponding cross-coupling products in high yields. Copyright

Iron(III) amine-bis(phenolate) complexes as catalysts for the coupling of alkyl halides with aryl Grignard reagents

Catalytic cross-coupling of aryl Grignard reagents with primary and secondary alkyl halides bearing β-hydrogens is achieved using Fe(III) amine-bis(phenolate) halide complexes. The Royal Society of Chemistry.

Cobalt(diamine)-catalyzed cross-coupling reaction of alkyl halides with arylmagnesium reagents: Stereoselective constructions of arylated asymmetric carbons and application to total synthesis of AH13205

A cobalt-diamine complex catalyzes the cross-coupling reactions of primary and secondary alkyl halides with aryl Grignard reagents. It is confirmed that oxidative addition of alkyl halide to cobalt proceeds via a radical process. Optically pure Ueno-Stork halo acetals undergo diastereoselective cross-coupling reactions, the products of which are transformed into optically active THF derivatives. A sequential radical cyclization/arylation reaction under cobalt catalysis provides extremely short access to a synthetic prostaglandin AH13205.

Iron-catalyzed grignard cross-coupling with alkyl halides possessing β-hydrogens

Tris(acetylacetonato)iron(III) (Fe(acac)3) was found to be an efficient catalyst for the cross-coupling reaction between aryl Grignard reagents and alkyl halides possessing β-hydrogens. The reaction is applicable to secondary alkyl halides as well as primary ones.