Access to Enantiomerically Pure P-Stereogenic Primary Aminophosphine Sulfides under Reductive Conditions.

Stereochemically pure phosphines with phosphorus-heteroatom bonds and P-centered chirality are a promising class of functional building blocks for the design of chiral ligands and organocatalysts. A route to enantiomerically pure primary aminophosphine sulfides was opened through stereospecific reductive C-N bond cleavage of phosphorus(V) precursors by lithium in liquid ammonia. The chemoselectivity of the reaction as a function of reaction time, substrate pattern, and chiral auxiliary was investigated.

Hidden silylium-type reactivity of a siloxane-based phosphonium-hydroborate ion pair.

A new class of siloxane-based cations with hidden silylium-type reactivity is provided, which, in combination with an arylborate counteranion, initiates a highly selective -C(sp)-F defunctionalization of a perfluorinated aryl group. The hydrodefluorinated aryl borane is obtained as a crystalline solid continuous sublimation during the reaction. The heterocyclic six-membered cation could be obtained single-crystalline after dehydrogenative anion exchange.

Easy Access to Enantiomerically Pure Heterocyclic Silicon-Chiral Phosphonium Cations and the Matched/Mismatched Case of Dihydrogen Release.

Phosphonium ions are widely used in preparative organic synthesis and catalysis. The provision of new types of cations that contain both functional and chiral information is a major synthetic challenge and can open up new horizons in asymmetric cation-directed and Lewis acid catalysis. We discovered an efficient methodology towards new Si-chiral four-membered CPSSi* heterocyclic cations.

Complexation behaviour of LiCl and LiPF- model studies in the solid-state and in solution using a bidentate picolyl-based ligand.

Structural knowledge on ubiquitous lithium salts in solution and in the crystalline state is of paramount importance for our understanding of many chemical reactions and of the electrolyte behaviour in lithium ion batteries. A bulky bidentate Si-based ligand (6) was used to create simplified model systems suitable for correlating structures of LiCl and LiPF complexes in the solid-state and in solution by combining various experimental, spectroscopic, and computational methods. Solution studies were performed using H DOSY, multinuclear variable temperature NMR spectroscopy, and quantum chemical calculations.

CO activation by manganese pincer complexes through different modes of metal-ligand cooperation.

We report here the activation of CO2 using two Mn-PNN pincer complexes that can exhibit different modes of metal-ligand cooperation amido/amino mode that involves [1,2]-activation of CO2 and dearomatization/aromatization mode that involves [1,3]-activation of CO2. We also compare their catalytic activity for CO2 hydrogenation.

Direct Synthesis of Amides by Acceptorless Dehydrogenative Coupling of Benzyl Alcohols and Ammonia Catalyzed by a Manganese Pincer Complex: Unexpected Crucial Role of Base.

Amide synthesis is one of the most important transformations in chemistry and biology. The direct use of ammonia for the incorporation of nitrogen functionalities in organic molecules is an attractive and environmentally benign method. We present here a new synthesis of amides by acceptorless dehydrogenative coupling of benzyl alcohols and ammonia.

Synthesis of Pyrazines and Quinoxalines via Acceptorless Dehydrogenative Coupling Routes Catalyzed by Manganese Pincer Complexes.

Base-metal catalyzed dehydrogenative self-coupling of 2-amino alcohols to selectively form functionalized 2,5-substituted pyrazine derivatives is presented. Also, 2-substituted quinoxaline derivatives are synthesized by dehydrogenative coupling of 1,2-diaminobenzene and 1,2-diols. In both cases, water and hydrogen gas are formed as the sole byproducts.

Manganese Catalyzed Hydrogenation of Organic Carbonates to Methanol and Alcohols.

The first example of a homogeneous catalyst based on an earth-abundant metal for the hydrogenation of organic carbonates to methanol and alcohols is reported. Based on the mechanistic investigation, which indicates metal-ligand cooperation between the manganese center and the N-H group of the pincer ligand, we propose that the hydrogenation of organic carbonates to methanol occurs via formate and aldehyde intermediates. The reaction offers an indirect route for the conversion of CO to methanol, which coupled with the use of an earth abundant catalyst, makes the overall process environmentally benign and sustainable.

Selective Hydrogenation of Cyclic Imides to Diols and Amines and Its Application in the Development of a Liquid Organic Hydrogen Carrier.

Direct hydrogenation of a broad variety of cyclic imides to diols and amines using a ruthenium catalyst is reported here. We have applied this strategy toward the development of a new liquid organic hydrogen carrier system based on the hydrogenation of bis-cyclic imide that is formed by the dehydrogenative coupling of 1,4-butanediol and ethylenediamine using a new ruthenium catalyst. The rechargeable system has a maximum gravimetric hydrogen storage capacity of 6.

Direct Synthesis of Amides by Dehydrogenative Coupling of Amines with either Alcohols or Esters: Manganese Pincer Complex as Catalyst.

The first example of base-metal-catalysed synthesis of amides from the coupling of primary amines with either alcohols or esters is reported. The reactions are catalysed by a new manganese pincer complex and generate hydrogen gas as the sole byproduct, thus making the overall process atom-economical and sustainable.

Synthesis of Cyclic Imides by Acceptorless Dehydrogenative Coupling of Diols and Amines Catalyzed by a Manganese Pincer Complex.

The first example of base-metal-catalyzed dehydrogenative coupling of diols and amines to form cyclic imides is reported. The reaction is catalyzed by a pincer complex of the earth abundant manganese and forms hydrogen gas as the sole byproduct, making the overall process atom economical and environmentally benign.

Manganese-Catalyzed Hydrogenation of Esters to Alcohols.

Homogeneous catalytic hydrogenation of esters to alcohols is an industrially important, environmentally benign reaction. While precious metal-based catalysts for this reaction are now well known, only very few catalysts based on first-row metal complexes were reported. Here we present the hydrogenation of esters catalyzed by a complex of earth-abundant manganese.

A case study of proton shuttling in palladium catalysis.

The mechanism of alkynoic acid cycloisomerization with SCS indenediide Pd pincer complexes has been investigated experimentally and computationally. These studies confirmed the cooperation between the Pd center and the backbone of the pincer ligand, and revealed the involvement of a second molecule of substrate. It acts as a proton shuttle in the activation of the acid, it directs the nucleophilic attack of the carboxylic acid on the π-coordinated alkyne and it relays the protonolysis of the resulting vinyl Pd species.

Manganese-Catalyzed Environmentally Benign Dehydrogenative Coupling of Alcohols and Amines to Form Aldimines and H2: A Catalytic and Mechanistic Study.

The catalytic dehydrogenative coupling of alcohols and amines to form aldimines represents an environmentally benign methodology in organic chemistry. This has been accomplished in recent years mainly with precious-metal-based catalysts. We present the dehydrogenative coupling of alcohols and amines to form imines and H2 that is catalyzed, for the first time, by a complex of the earth-abundant Mn.