Magnesium–Ligand Cooperation Enables Regioselective Transfer Hydrogenation of Quinolines to 1,2-Dihydroquinolines

We report the first magnesium-catalyzed regioselective reduction of quinolines to 1,2-dihydroquinolines, utilizing H3N·BH3. This protocol operates under mild conditions and tolerates a broad range of ...

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Carbene Analogues of Group 15: Reduction of s-Hydrindacene-Based Chloropnictogenium Ions To Access an Antimony Hydride Monocation and a Trinuclear Bismuth Dication

We report the synthesis of three chloropnictogenium cations [MSFluindECl]+ (2As, 2Sb and 2 Bi), which unravel different reaction pathways toward Et3SiH, leading to the formation of the neutral arylars...

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Magnesium–Ligand Cooperation Enables Regioselective Transfer Hydrogenation of Quinolines to 1,2-Dihydroquinolines

We report the first magnesium-catalyzed regioselective reduction of quinolines to 1,2-dihydroquinolines, utilizing H3N·BH3. This protocol operates under mild conditions and tolerates a broad range of ...

pubs.acs.org

Magnesium-Catalyzed CO2 Reduction to Formic Acid or Methanol: Solvent or No Solvent Settles the Selectivity

Reducing the carbonyl (C═O) group in carbon dioxide is a difficult yet crucial step for producing valuable chemical compounds. This approach holds promise for creating new methods to utilize nonfossil-based raw materials. Using catalysts made from abundant, inexpensive, and environmentally friendly metals, such as magnesium, could significantly advance the development of sustainable synthetic techniques. In this study, a magnesium pincer compound (1) is shown to facilitate the reduction of CO2 with pinacolborane as the reductant. When used without a solvent, the reaction produces methoxyborane, whereas in THF, it leads to formoxyborane. Formoxyborane has been identified as a “missing link” in homogeneous CO2 reduction by catalysts based on alkaline earth metal elements. The variation in product selectivity was substantiated through DFT calculations. The initial generation of the Mg(II) hydride catalyst both in the absence and presence of THF entails an activation barrier within 25–26 kcal mol–1. However, the rate-determining step, in the absence of a solvent, involves hydride transfer-mediated reduction at the formate fragment accompanying a transition barrier of 27.3 kcal mol–1. In the presence of THF, the rate-determining step involves hydride transfer to the Mg center with a barrier of 29.2 kcal mol–1, generating the catalyst and boryl formate.

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A Kekulé Diradicaloid with a Naphthalene Spacer

The availability of a diverse array of carbenes led to the generation of a catalog of carbene based Kekulé diradicaloids, but the linker in such molecules is mostly limited to phenylene or biphenylene...

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Diaryl Bismuthides and Acyl Bismuthanes Enable Visible-Light-Induced Reversible Carbon Monoxide Insertion and Extrusion - Nature Communications

Carbon monoxide (CO) is one of the simplest and most fundamental molecules that has fascinated chemists for decades. Early-on, chemists have recognized and exploited its favorable properties as a key ...

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Reversible C–H Bond Activation of Unactivated Arenes by a Nickel-Silylene Complex

A nickel-silylene complex is shown to reversibly activate benzene via C–H bond activation at ambient temperature. The benzene C–H bond formally adds across the Ni–Si core to form a nickel-silyl comple...

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Magnesium-Catalyzed Primary, Secondary, and Tertiary Amide Hydroboration

Catalytic hydroboration of amides is highly important because the resultant amines are commonly found in natural products, pharmaceuticals, agrochemicals, dyes, and other applications. In comparison to the conventional reduction of amides using (over)stoichiometric reductants, hydroboration of amides using magnesium compounds represents a green and sustainable approach because magnesium is both Earth abundant and environmentally benign. However, there is only one report on magnesium-catalyzed deoxygenative hydroboration of secondary and tertiary amides. Here, we describe the synthesis and structural authentication of two new magnesium compounds (1 and 2) featuring a flexible PNP ligand and the utilization of 2 as a catalyst for the pinacolborane-mediated reduction of primary, secondary, and tertiary amides to amines. The reaction scope is explored, and a mechanism is proposed based on experimental and theoretical insights.

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Manganese(I)-catalyzed dehydrogenative borylation of terminal alkynes

Compounds containing carbon–boron bonds serve as valuable intermediates for constructing more complex molecules by transforming these bonds into other carbon–element bonds. The catalytic dehydrogenati...

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Sila[1]ferrocenophanes with Bulky Substituents

Nucleophilic substitution via selective removal of one chlorine atom of dichlorosila[1]ferrocenophane using various reagents to yield novel sila[1]ferrocenophanes with sterically bulky groups.

chemistry-europe.onlinelibrary.wiley.com

Synthesis of Diamido N-Heterocyclic Imines (DAC = NH) Via Staudinger or Reductive N–N Bond Cleavage Approach

This report communicates the first examples of N-heterocyclic imines based on electrophilic diamido carbenes (DACs). While 2 is prepared by classical Staudinger synthesis, 4 is obtained via an unusua...

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The Careful Combination of Bismuth Compounds and CAAC: Formal Halonium and Nitrenium Transfer via Radical Pathways

Fundamental bismuth compounds such as BiCl3 and BiBr(NMe2)2 form simple, colorful adducts with cyclic (alkyl)(amino)carbenes. They undergo facile and selective formal X+ and (NMe2)+ transfer from bis...

chemistry-europe.onlinelibrary.wiley.com

Development of six-membered saturated cyclic diaminocarbenes in main-group chemistry

In recent years, there has been a remarkable surge in the utilization of saturated N-heterocyclic carbenes (NHCs) as ligands in main group chemistry. While the field has predominantly focused on five-...

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Magnesium–Ligand Cooperation in Breaking the O–H and C–H Bonds of Water and Diazoalkane

In our previous paper, we reported that the reaction of a tridentate nacnac ligand with a pendant picolyl group, with KHMDS and MgI2, resulted in the formation of a homoleptic hexacoordinate magnesium...

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Germylene Mediated Reductive C−C and C−N Coupling of an Isocyanide and its Device Application

Reductive coupling of perimidine based N-heterocyclic germylene and 4-iodophenyl isocyanide afforded a highly colored and luminescent bis-spirogerma species with unprecedented simultaneous C−N and C−....

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Germylene Mediated Reductive C−C and C−N Coupling of an Isocyanide and its Device Application

Reductive coupling of perimidine based N-heterocyclic germylene and 4-iodophenyl isocyanide afforded a highly colored and luminescent bis-spirogerma species with unprecedented simultaneous C−N and C−....

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Unprecedented C–F bond cleavage in perfluoronaphthalene during cobaltocene reduction

The C–F bond activation of perfluoronaphthalene by 5-SIDipp led to the formation of dicationic salts with two fluorides (3·2HF2 ) or heptafluorodiborate (3·2B2F7) as counter-anions. The anion exchange...

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Uncovering diverse reactivity of NHCs with diazoalkane: C–H activation, CC bond formation, and access to N-heterocyclic methylenehydrazine

N-heterocyclic carbenes (NHCs) have attracted significant attention due to their strong σ-donating capabilities, as well as their transition-metal-like reactivity towards small molecules. However, the...

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