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Upstream product

• 32960-45-5 1-(4-methoxyphenyl)cyclohept-1-ene 
• 2404-35-5 cycloheptyl bromide 
• 699-19-4 4-methoxyphenylmagnesium chloride 
• 97302-05-1 di-4-methoxyphenylzinc 
• 104-92-7 1-bromo-4-methoxy-benzene 
• 628-92-2 Cycloheptene 
• 502-42-1 cycloheptanone 
• 171364-79-7 2-(4-methoxyphenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane 

Downstream Products

• 75120-08-0 4-cycloheptylphenol 

Relevant academic research and scientific papers

Air-Stable Iron-Based Precatalysts for Suzuki-Miyaura Cross-Coupling Reactions between Alkyl Halides and Aryl Boronic Esters

The development of an air-stable iron(III)-based precatalyst for the Suzuki-Miyaura cross-coupling reaction of alkyl halides and unactivated aryl boronic esters is reported. Despite benefits to cost and toxicity, the proclivity of iron(II)-based complexes to undergo deactivationviaoxidation or hydrolysis is a limiting factor for their widespread use in cross-coupling reactions compared to palladium-based or nickel-based complexes. The new octahedral iron(III) complex demonstrates long-term stability on the benchtop as assessed by a combination of1H NMR spectroscopy, M?ssbauer spectroscopy, and its sustained catalytic activity after exposure to air. The improved stability of the iron-based catalyst facilitates an improved protocol in which Suzuki-Miyaura cross-coupling reactions of valuable substrates can be assembled without the use of a glovebox and access a diverse scope of products similar to reactions assembled in the glovebox with iron(II)-based catalysts.

Decarboxylative Negishi Coupling of Redox-Active Aliphatic Esters by Cobalt Catalysis

A cobalt-catalyzed decarboxylative Negishi coupling reaction of redox-active aliphatic esters with organozinc reagents was developed. The method enabled efficient alkyl–aryl, alkyl–alkenyl, and alkyl–alkynyl coupling reactions under mild reaction conditions with no external ligand or additive needed. The success of an in situ activation protocol and the facile synthesis of the drug molecule (±)-preclamol highlight the synthetic potential of this method. Mechanistic studies indicated that a radical mechanism is involved.

Iron-Catalyzed Suzuki-Miyaura Cross-Coupling Reactions between Alkyl Halides and Unactivated Arylboronic Esters

An iron-catalyzed cross-coupling reaction between alkyl halides and arylboronic esters was developed that does not involve activation of the boronic ester with alkyllithium reagents nor requires magnesium additives. A combination of experimental and theoretical investigations revealed that lithium amide bases coupled with iron complexes containing deprotonated cyanobis(oxazoline) ligands were best to obtain high yields (up to 89%) in catalytic cross-coupling reactions. Mechanistic investigations implicate carbon-centered radical intermediates and highlight the critical importance of avoiding conditions that lead to iron aggregates. The new iron-catalyzed Suzuki-Miyaura reaction was applied toward the shortest reported synthesis of the pharmaceutical Cinacalcet.

A Dual Palladium and Copper Hydride Catalyzed Approach for Alkyl–Aryl Cross-Coupling of Aryl Halides and Olefins

We report an efficient means of sp2–sp3 cross coupling for a variety of terminal monosubstituted olefins with aryl electrophiles using Pd and CuH catalysis. In addition to its applicability to a range of aryl bromide substrates, this process was also suitable for electron-deficient aryl chlorides, furnishing higher yields than the corresponding aryl bromides in these cases. The optimized protocol does not require the use of a glovebox and employs air-stable Cu and Pd complexes as precatalysts. A reaction on 10 mmol scale further highlighted the practical utility of this protocol. Employing a similar protocol, a series of cyclic alkenes were also examined. Cyclopentene was shown to undergo efficient coupling under these conditions. Lastly, deuterium-labeling studies indicate that deuterium scrambling does not take place in this sp2-sp3 cross coupling, implying that β-hydride elimination is not a significant process in this transformation.

Expedient iron-catalyzed coupling of alkyl, benzyl and allyl halides with arylboronic esters

While attractive, the iron-catalyzed coupling of arylboron reagents with alkyl halides typically requires expensive or synthetically challenging diphosphine ligands. Herein, we show that primary and secondary alkyl bromides and chlorides, as well as benzyl and allyl halides, can be coupled with arylboronic esters, activated with alkyllithium reagents, by using very simple iron-based catalysts. The catalysts used were either adducts of inexpensive and widely available diphosphines or, in a large number of cases, simply [Fe(acac)3] with no added co- ligands. In the former case, preliminary mechanistic studies highlight the likely involvement of iron(I)-phosphine intermediates. More irons in the fire: Primary and secondary alkyl, benzyl and allyl halides were coupled with arylboronic esters by using very simple iron-based catalysts. These were either adducts of inexpensive and widely available diphosphines or, in a large number of cases, simply [Fe(acac)3] with no added co-ligands (see scheme; acac=acetylacetonate). In the former case, preliminary mechanistic studies highlight the likely involvement of low-coordinate iron(I)-phosphine intermediates.

CATALYST FOR CROSS-COUPLING REACTION, AND PROCESS FOR PRODUCTION OF AROMATIC COMPOUND USING THE SAME

The present invention provides a process for efficiently producing an alkylated aromatic compound in good yield, by a cross-coupling reaction between an alkyl halide and an aromatic magnesium reagent. A process for producing an aromatic compound represented by Formula (1): [in-line-formulae]R—Ar′??(1)[/in-line-formulae]wherein R is a hydrocarbon group, and Ar′ is an aryl group;the process comprising:reacting a compound represented by Formula (2): [in-line-formulae]R—X??(2)[/in-line-formulae]wherein X is a halogen atom, and R is as defined above, with a magnesium reagent represented by Formula (3): [in-line-formulae]Ar′—MgY??(3)[/in-line-formulae]wherein Y is a halogen atom, and Ar′ is as defined above, in the presence of a catalyst for cross-coupling reactions comprising an iron compound and a bisphosphine compound represented by Formula (4): wherein Q is a divalent group derived from an aromatic ring by removing two hydrogen (H) atoms on adjacent carbon atoms; and each Ar is independently an aryl group.

The first iron-catalysed aluminium-variant Negishi coupling: Critical effect of co-existing salts on the dynamic equilibrium of arylaluminium species and their reactivity

The first example of an iron-catalysed Negishi coupling between arylaluminium reagents and alkyl halides illustrates that the co-existing salts highly influence the dynamic equilibrium of the organoaluminium species, and have a critical effect on the reactivity and selectivity of the coupling reaction.

Iron-catalyzed Suzuki-Miyaura coupling of alkyl halides

In the presence of novel iron(II) chloride-diphosphine complexes and magnesium bromide, lithium arylborates react with primary and secondary alkyl halides to give the corresponding coupling products in good to excellent yields. High functional group compa