Synthesis of homoleptic Re(I) complexes of isocyano-carboranes and the X-ray structure of hexakis(p-carboran-1-yl-isonitrile)Re(I)

Two homoleptic Re(I) complexes of ortho and para-carborane isocyanide ligands were prepared as the first examples of a new class of metal-based BNCT and BNCS agents. The target compounds were prepared in low yield through the reaction of [Re₂(O₂CPh)₄Cl₂] and [Re₂(OAc)₄Cl₂] with 3-isocyano-1,2-dicarba-closo-dodecaborane and a para-carborane azetidine derivative respectively. The desired product from the latter reaction was characterized crystallographically and is only the second reported molecular structure of a homoleptic Re(I) isonitrile complex.     

Synthesis of α-carboranyl-α-acyloxy-amides as potential BNCT agents

Novel α-carboranyl-α-acyloxy-amides were prepared as potential BNCT agents utilizing three-component Passerini reaction. Preliminary cytotoxicity of the representative compounds on two brain tumor cell lines (U-87 and A-172) showed no effect on cell viability; an essential requirement for utility as potential BNCT agents.     

Oligomerisierung von Nitrilen und Isonitrilen mittels Metallanen und geminalen Dilithiumverbindungen

Oligomerizations of Nitriles and Isonitriles with Metallanes and Geminal Dilithium Compounds The reactions of nitriles and isonitriles with metallanes of group 13 and geminal dilithium compounds, preferably ^tBuELi₂ (E = P, As), will be introduced. The results from investigations concerning intermediates and products exhibit partly significant differences to known reaction systems from transition metal chemistry.     

Facile reaction of carboxylic acids with isonitriles in toluene

Isonitriles react with low concentrations of carboxylic acids in toluene at 110 °C to give N-formylamides in yields generally above 70%. These concentrations can be obtained either by syringe pump addition of a toluene solution of the acid, or by using a suspension of the acid if it has limited solubility in toluene at room temperature.     

A Simple, General Synthesis of Carbonimidic Dichlorides

The reaction of aliphatic and aromatic isonitriles with sulfuryl chloride provides an efficient, general route to the corresponding dichlorides without byproducts of free-radical substitution.     

First Diastereoselective PasseriniSmiles and UgiSmiles Reactions Using Chiral Aldehydes

A diastereoselective O/N‐arylative Passerini/Ugi reaction of chiral aldehydes with commercially available isocyanides affording O‐aryl amides and N‐aryl amides, respectively, as products in moderate to good yields, together with de values, is reported.     

An efficient boric acid-mediated preparation of α-hydroxyamides

An efficient methodology for the preparation of α-hydroxyamides via boric acid-mediated addition of isonitriles onto aldehydes has been developed. The reaction of isonitriles with α-boronobenzaldehyde takes place under intramolecular catalysis conditions to provide functionalized benzoxaboroles.     

A new, modular approach towards 2-(1-hydroxyalkyl)oxazolines, effective bidentate chiral ligands

Addition of β-hydroxyisonitriles towards aldehydes gives rise to hydroxyalkyl oxazolines, an interesting class of bidentate chiral ligands. This concept allows a very easy ligand tuning and optimization of the ligand structure as illustrated in a first example.     

Direct synthesis of 6-sulfonylated phenanthridines via silver-catalyzed radical sulfonylation-cyclization of 2-isocyanobiphenyls

A convenient and straightforward synthesis of 6-sulfonylated phenanthridines via silver-catalyzed sequential radical insertion, cyclization and aromatization of 2-isocyanobiphenyls is reported. The protocol does not require a phenanthridine scaffold as a substrate and presents a highly regioselective synthesis of 6-alkyl/arylsulfonyl phenanthridines. The protocol utilizes readily available and easy to handle sodium sulfinates as sulfonating agents and potassium persulfate as an oxidant to afford good to excellent yields of the desired products in a one-pot operation at room temperature.     

Reaction of N-fluoropyridinium fluoride with isonitriles and TMSN3: a convenient one-pot synthesis of tetrazol-5-yl pyridines

Reaction of N-fluoropyridinium fluoride generated in situ with a series of isonitriles and TMSN₃ led to the formation of the corresponding tetrazol-5-yl pyridines in good yields (37-84%). A similar reaction sequence for quinoline yielded the respective derivatives of 2-quinoline. The proposed reaction mechanism involves the intermediate formation of a highly reactive carbene species.