James Sanderson

A catalytic system consisting of CoCl₂⋅2 LiCl (5 mol %) and HCO₂Na (50 mol %) enables the cross-coupling of various N-heterocyclic chlorides and bromides as well as aromatic halogenated ketones with various electron-rich and -poor arylzinc reagents. The reactions reached full conversion within a few hours at 25 °C.

May the formate be with you! A simple, practical cobalt salt catalyzed procedure for cross-coupling reactions of halogenated ketones as well as N-heterocyclic chlorides and bromides with various electron-rich and -poor (hetero)arylzinc reagents was developed. The addition of sodium formate is essential for the efficiency of this cross-coupling. TBS=tert-butyldimethylsilyl.

A set of S-adenosyl-l-methionine (SAM) dependent methyltransferases has been characterized as versatile catalysts for the enzymatic Friedel–Crafts (alkylation) reaction. Although the substrate specificity of the enzymes range from high (in the case of SfmM2, SacF, and ORF19) to moderate (in the case of NovO and CouO), the cofactor spectrum is broad. Modified cofactors decorated with alkyl groups other than methyl were used for biocatalytic Friedel–Crafts alkylation, and conversions up to 99 % were achieved. In contrast to the classical chemical reaction the biotransformation is very selective and environmentally compatible.

Arts and Friedel–Crafts: A set of S-adenosyl-l-methionine (SAM) dependent methyltransferases as versatile catalysts for the enzymatic Friedel–Crafts (alkylation) reaction is characterized. Modified cofactors decorated with alkyl groups other than methyl are used for biocatalytic Friedel–Crafts alkylation, and conversions up to 99 % are achieved. In contrast to the classical chemical reaction the biotransformation is very selective and environmentally compatible.

Methylation of C(sp²)−H bonds was achieved through the Ni^II-catalyzed reaction of benzamides with phenyltrimethylammonium bromide or iodide as the source of the methyl group. The reaction has a broad scope and shows high functional-group compatibility. The reaction is also applicable to the methylation of C(sp³)−H bonds in aliphatic amides.

Its all about Me! The methylation of C(sp²)−H bonds was achieved through the Ni^II-catalyzed reaction of benzamides with phenyltrimethylammonium bromide or iodide as the source of the methyl group. The reaction has a broad scope and shows high functional-group compatibility. The reaction is also applicable to the methylation of C(sp³)−H bonds in aliphatic amides.

A graphical analysis to elucidate the order in catalyst is presented. This analysis uses a normalized time scale, t [cat]_Tⁿ, to adjust entire reaction profiles constructed with concentration data. The method is fast and simple to perform because it directly uses the concentration data, therefore avoiding the data handling that is usually required to extract rates. Compared to methods that use rates, the normalized time scale analysis requires fewer experiments and minimizes the effects of experimental errors by using information on the entire reaction profile.

A graphical analysis to elucidate the order in catalyst uses a normalized time scale, t [cat]_Tⁿ, to adjust entire reaction profiles constructed with concentration data. Compared to methods that use rates, the normalized time scale analysis requires fewer experiments and minimizes the effects of experimental errors by using information on the entire reaction profile.

Nickel-catalyzed selective cross-coupling of aromatic electrophiles (bromides, chlorides, fluorides and methyl ethers) with organolithium reagents is presented. The use of a commercially available nickel N-heterocyclic carbene (NHC) complex allows the reaction with a variety of (hetero)aryllithium compounds, including those prepared via metal-halogen exchange or direct metallation, whereas a commercially available electron-rich nickel-bisphosphine complex smoothly converts alkyllithium species into the corresponding coupled product. These reactions proceed rapidly (1 h) under mild conditions (room temperature) while avoiding the undesired formation of reduced or homocoupled products.

Nickel-catalyzed cross-coupling of aromatic electrophiles with organolithium reagents is presented. The use of a commercially available nickel N-heterocyclic carbene complex allows reaction with a variety of (hetero)aryllithium compounds, whereas a commercially available electron-rich nickel bisphosphine complex smoothly converts alkyllithium species into the corresponding coupled product.