41876-58-8

Upstream product

• 626-62-0 Cyclohexyl iodide 
• 100-66-3 methoxybenzene 
• 75-05-8 acetonitrile 
• 110-83-8 cyclohexene 
• 1027527-21-4 imidazole-1-carbothioic acid O-[1-(3-methoxy-phenyl)-hex-5-enyl] ester 
• 2845-89-8 1-chloro-3-methoxy-benzene 
• 446065-11-8 cyclohexyltrifluoro-λ⁴-borane potassium salt 
• 108-85-0 1-bromocyclohexane 
• 2398-37-0 3-methoxyphenyl bromide 
• 1003858-50-1 2-(3-methoxyphenyl)-5, 5-dimethyl-1,3,2-dioxaborinane 
• 256390-55-3 cyclohexylzinc chloride 
• 931-50-0 cyclohexylmagnesium bromide 
• 110-82-7 cyclohexane 
• 36282-40-3 (3-methoxyphenyl)magnesium bromide 

Downstream Products

• 1943-95-9 meta-cyclohexylphenol 
• 57568-38-4 1-(4-cyclohexyl-2-methoxyphenyl)ethan-1-one 
• 66883-53-2 (4-Cyclohexyl-2-hydroxy-5-methyl-phenyl)-acetic acid 
• 66883-45-2 3-bromo-4-cyclohexyl-2-hydroxyphenylacetic acid 
• 66883-50-9 5-Chloro-4-cyclohexyl-2-hydroxy-α-methyl-phenylacetic acid 
• 66883-44-1 4-cyclohexyl-2-hydroxy-5-nitrophenylacetic acid 
• 57568-37-3 6-cyclohexyl-2,3-dihydrobenzofuran-2-one 
• 60986-91-6 7-bromo-6-cyclohexyl-2,3-dihydrobenzofuran-2-one 
• 60986-96-1 6-cyclohexyl-2,3-dihydro-5-methylbenzofuran-2-one 
• 60986-93-8 5-chloro-6-cyclohexyl-2,3-dihydro-3-methylbenzofuran-2-one 
• 60986-89-2 5-chloro-6-cyclohexyl-2,3-dihydrobenzofuran-2-one 
• 60986-90-5 5-bromo-6-cyclohexyl-2,3-dihydrobenzofuran-2-one 
• 79380-80-6 4-cyclohexyl-2-methoxy-5-methylphenylacetic acid 
• 79380-75-9 ethyl 4-cyclohexyl-2-methoxy-α-methylphenylacetate 

Relevant academic research and scientific papers

Cobalt-Catalyzed C(sp2)-C(sp3) Suzuki-Miyaura Cross-Coupling Enabled by Well-Defined Precatalysts with L,X-Type Ligands

Cobalt(II) halides in combination with phenoxyimine (FI) ligands generated efficient precatalysts in situ for the C(sp2)-C(sp3) Suzuki-Miyaura cross-coupling between alkyl bromides and neopentylglycol (hetero)arylboronic esters. The protocol enabled efficient C-C bond formation with a host of nucleophiles and electrophiles (36 examples, 34-95%) with precatalyst loadings of 5 mol %. Studies with alkyl halide electrophiles that function as radical clocks support the intermediacy of alkyl radicals during the course of the catalytic reaction. The improved performance of the FI-cobalt catalyst was correlated with decreased lifetimes of cage-escaped radicals as compared to those of diamine-type ligands. Studies of the phenoxyimine-cobalt coordination chemistry validate the L,X interaction leading to the discovery of an optimal, well-defined, air-stable mono-FI-cobalt(II) precatalyst structure.

Mechanical metal activation for Ni-catalyzed, Mn-mediated cross-electrophile coupling between aryl and alkyl bromides

Liquid-assisted grinding has been successfully applied to eliminate the requirements of chemical activators and anhydrous solvents in nickel-catalyzed, manganese-mediated cross-electrophile coupling between aryl and alkyl bromides. In addition to the traditional reaction parameters, mechanical ones,e.g.the rotational speed of mill, the filling degree of jar and ball size, have been found to affect the catalytic efficiency remarkably, implying the involvement of the regeneration of nickel(0) species in the rate-determining steps. A combined evaluation of the reaction and mechanical parameters led to an optimal condition under which a variety ofn-alky aromatics with various functional groups could be readily obtained in good yields with a 1 mol% catalyst loading. The practical application of liquid-assisted grinding-enabled aryl/alkyl cross-electrophile coupling has been demonstrated in the gram-scale synthesis of 6-methoxytetralone.

Dilithium Amides as a Modular Bis-Anionic Ligand Platform for Iron-Catalyzed Cross-Coupling

Dilithium amides have been developed as a bespoke and general ligand for iron-catalyzed Kumada-Tamao-Corriu cross-coupling reactions, their design taking inspiration from previous mechanistic and structural studies. They allow for the cross-coupling of alkyl Grignard reagents with sp2-hybridized electrophiles as well as aryl Grignard reagents with sp3-hybridized electrophiles. This represents a rare example of a single iron-catalyzed system effective across diverse coupling reactions without significant modification of the catalytic protocol, as well as remaining operationally simple.

Coupling of Reformatsky Reagents with Aryl Chlorides Enabled by Ylide-Functionalized Phosphine Ligands

The coupling of aryl chlorides with Reformatsky reagents is a desirable strategy for the construction of α-aryl esters but has so far been substantially limited in the substrate scope due to many challenges posed by various possible side reactions. This limitation has now been overcome by the tailoring of ylide-functionalized phosphines to fit the requirements of Negishi couplings. Record-setting activities were achieved in palladium-catalyzed arylations of organozinc reagents with aryl electrophiles using a cyclohexyl-YPhos ligand bearing an ortho-tolyl-substituent in the backbone. This highly electron-rich, bulky ligand enables the use of aryl chlorides in room temperature couplings of Reformatsky reagents. The reaction scope covers diversely functionalized arylacetic and arylpropionic acid derivatives. Aryl bromides and chlorides can be converted selectively over triflate electrophiles, which permits consecutive coupling strategies.

Visible-Light-Promoted Iron-Catalyzed C(sp2)–C(sp3) Kumada Cross-Coupling in Flow

A continuous-flow, visible-light-promoted method has been developed to overcome the limitations of iron-catalyzed Kumada–Corriu cross-coupling reactions. A variety of strongly electron rich aryl chlorides, previously hardly reactive, could be efficiently coupled with aliphatic Grignard reagents at room temperature in high yields and within a few minutes’ residence time, considerably enhancing the applicability of this iron-catalyzed reaction. The robustness of this protocol was demonstrated on a multigram scale, thus providing the potential for future pharmaceutical application.

Sterically congested phosphonium borate acids as effective Br?nsted acid catalysts

Phosphonium borate acids [HPPh2(C6F5)][B(C6F5)4] (2), [HPMes2(C6F5)][B(C6F5)4] (3) and [HPMes(C6F5)2][B(C6F5)4] (4) were synthesized via heterolytic dihydrogen cleavage in the presence of triisopropylsilylium and characterized by spectroscopic and crystallographic methods. Br?nsted acid catalysis using compounds 2–4 proved to be efficient for a number of challenging reactions (namely ionic hydrogenation, hydroamination and hydroarylation), owing to the restrained nucleophilicity of the sterically hindered conjugate bases. Reactivity of compounds 2–4 suggests that their pKavalues are similar to that of diethyl oxonium acid.

NOVEL PRECATALYST SCAFFOLDS FOR CROSS-COUPLING REACTIONS, AND METHODS OF MAKING AND USING SAME

The present invention provides novel transition-metal precatalysts that are useful in preparing active coupling catalysts. In certain embodiments, the precatalysts of the invention are air-stable and moisture-stable. The present invention further provides methods of making and using the precatalysts of the invention.

Catalytic Asymmetric Hydroalkenylation of Vinylarenes: Electronic Effects of Substrates and Chiral N-Heterocyclic Carbene Ligands

An asymmetric tail-to-tail cross-hydroalkenylation of vinylarenes with terminal olefins was achieved by catalysis with NiH complexes bearing chiral N-heterocyclic carbenes (NHCs). The reaction provides branched gem-disubstituted olefins with high enantioselectivity (up to 94% ee) and chemoselectivity (cross/homo product ratio: up to 99:1). Electronic effects of the substituents on the vinylarenes and on the N-aryl groups of the NHC ligands, but not a π,π-stacking mechanism, assist the steric effect and influence the outcome of the cross-hydroalkenylation.

Design of a versatile and improved precatalyst scaffold for palladium-catalyzed cross-coupling: (η3-1-tBu-indenyl)2(μ-Cl)2Pd2

We describe the development of (η3-1-tBu-indenyl)2(μ-Cl)2Pd2, a versatile precatalyst scaffold for Pd-catalyzed cross-coupling. Our new system is more active than commercially available (η3-cinnamyl)2(μ-Cl)2Pd2 and is compatible with a range of NHC and phosphine ligands. Precatalysts of the type (η3-1-tBu-indenyl)Pd(Cl)(L) can either be isolated through the reaction of (η3-1-tBu-indenyl)2(μ-Cl)2Pd2 with the appropriate ligand or generated in situ, which offers advantages for ligand screening. We show that the (η3-1-tBu-indenyl)2(μ-Cl)2Pd2 scaffold generates highly active systems for a number of challenging cross-coupling reactions. The reason for the improved catalytic activity of systems generated from the (η3-1-tBu-indenyl)2(μ-Cl)2Pd2 scaffold compared to (η3-cinnamyl)2(μ-Cl)2Pd2 is that inactive PdI dimers are not formed during catalysis.

Stereospecific Pd-catalyzed cross-coupling reactions of secondary alkylboron nucleophiles and aryl chlorides

We report the development of a Pd-catalyzed process for the stereospecific cross-coupling of unactivated secondary alkylboron nucleophiles and aryl chlorides. This process tolerates the use of secondary alkylboronic acids and secondary alkyltrifluoroborates and occurs without significant isomerization of the alkyl nucelophile. Optically active secondary alkyltrifluoroborate reagents undergo cross-coupling reactions with stereospecific inversion of configuration using this method.