Mechanochemical Iron-Catalyzed Nitrene Transfer Reactions: Direct Synthesis of N-Acyl Sulfonimidamides from Sulfinamides and Dioxazolones.

A mechanochemical synthesis of sulfonimidamides by iron(II)-catalyzed exogenous ligand-free N-acyl nitrene transfer to sulfinamides is reported. The one-step method tolerates a wide range of sulfinamides with various substituents under solvent-free ambient conditions. Compared to its solution-phase counterpart, this mechanochemical approach shows better conversion and chemoselectivity. Mechanistic investigations by ESI-MS revealed the generation of crucial nitrene iron intermediates.

Diiminium Nucleophile Adducts Are Stable and Convenient Strong Lewis Acids.

Strong Lewis acids are essential tools for manifold chemical procedures, but their scalable deployment is limited by their costs and safety concerns. We report a scalable, convenient, and inexpensive synthesis of stable diiminium-based reagents with a Lewis acidic carbon centre. Coordination with pyridine donors stabilises these centres; the 2,2'-bipyridine adduct shows a chelation effect at carbon. Due to high fluoride, hydride, and oxide affinities, the diiminium pyridine adducts are promising soft and hard Lewis acids. They effectively produce acylpyridinium salts from carboxylates that can acylate amines to give amides and imides even from electronically intractable coupling partners.

How To Enhance the Efficiency of Breslow Intermediates for SET Catalysis.

Oxidative carbene organocatalysis, which proceeds via single electron transfer (SET) pathways, has been limited by the moderately reducing properties of deprotonated Breslow intermediates BI-s derived from thiazol-2-ylidene 1 and 1,2,4-triazolylidene 2. Using computational methods, we assess the redox potentials of BI-s based on ten different types of known stable carbenes and report our findings concerning the key parameters influencing the steps of the catalytic cycle. From the calculated values of the first oxidation potential of BI-s derived from carbenes 1 to 10, it appears that, apart from the diamidocarbene 7, all the others are more reducing than thiazol-2-ylidene 1 and the 1,2,4-triazolylidene 2. We observed that while the reducing power of BI-s significantly decreases with increasing solvent polarity, the redox potential of the oxidant can increase at a greater rate, thus facilitating the reaction. The cation, associated with the base, also plays an important role when a nonpolar solvent is used; large and weakly coordinating cations such as Cs+ are beneficial. The radical-radical coupling step is probably the most challenging step due to both electronic and steric constraints. Based on our results, we predict that mesoionic carbene 3 and abnormal NHC 4 are the most promising candidates for oxidative carbene organocatalysis.

Entropy-Induced Selectivity Switch in Gold Catalysis: Fast Access to Indolo[1,2-a]quinolines.

New N-heterocyclic compounds for organic functional materials and their efficient syntheses are highly demanded. A surprising entropy-induced selectivity switch in the gold-catalyzed intramolecular hydroarylation of 2-ethynyl N-aryl indoles was found and its exploitation led to straightforward syntheses of indolo[1,2-a]quinolines. Experimental and computational mechanistic investigations gave insight into this uncommon selectivity phenomenon and into the special reactivity of the indolo[1,2-a]quinolines. The high functional group tolerance of this methodology enabled access to a diverse scope with high yields. In addition, bidirectional approaches, post-functionalization reactions, and π-extension of the core structure were feasible. An in-depth study of the photophysical properties explored the structure-effect relationship for different derivatives and revealed a high potential of these compounds for future applications as functional materials.

Ultrafast amidation of esters using lithium amides under aerobic ambient temperature conditions in sustainable solvents.

Lithium amides constitute one of the most commonly used classes of reagents in synthetic chemistry. However, despite having many applications, their use is handicapped by the requirement of low temperatures, in order to control their reactivity, as well as the need for dry organic solvents and protective inert atmosphere protocols to prevent their fast decomposition. Advancing the development of air- and moisture-compatible polar organometallic chemistry, the chemoselective and ultrafast amidation of esters mediated by lithium amides is reported. Establishing a novel sustainable access to carboxamides, this has been accomplished via direct C-O bond cleavage of a range of esters using glycerol or 2-MeTHF as a solvent, in air. High yields and good selectivity are observed while operating at ambient temperature, without the need for transition-metal mediation, and the protocol extends to transamidation processes. Pre-coordination of the organic substrate to the reactive lithium amide as a key step in the amidation processes has been assessed, enabling the structural elucidation of the coordination adduct [{Li(NPh2)(O[double bond, length as m-dash]CPh(NMe2))}2] (8) when toluene is employed as a solvent. No evidence for formation of a complex of this type has been found when using donor THF as a solvent. Structural and spectroscopic insights into the constitution of selected lithium amides in 2-MeTHF are provided that support the involvement of small kinetically activated aggregates that can react rapidly with the organic substrates, favouring the C-O bond cleavage/C-N bond formation processes over competing hydrolysis/degradation of the lithium amides by moisture or air.

Ambient Moisture Accelerates Hydroamination Reactions of Vinylarenes with Alkali-Metal Amides under Air.

A straightforward alkali-metal-mediated hydroamination of styrenes using biorenewable 2-methyltetrahydrofuran as a solvent is reported. Refuting the conventional wisdom of the incompatibility of organolithium reagents with air and moisture, shown here is that the presence of moisture is key in favoring formation of the target phenethylamines over competing olefin polymerization products. The method is also compatible with sodium amides, with the latter showing excellent promise as highly efficient catalysts under inert atmosphere conditions.

Dibenzothiophenesulfilimines: A Convenient Approach to Intermolecular Rhodium-Catalysed C-H Amidation.

A sulfilimine-based Group 9 transition-metal-catalysed C-H amidation procedure is reported. Dibenzothiophene-based sulfilimines were shown to constitute a class of novel amidation reagents which enable the transfer of a wide range of N-sulfonyl and N-acyl moieties. It was demonstrated that sulfilimines, which are easily accessible from cheap reagents, are safe-to-handle and represent broadly applicable amidation reagents. The dibenzothiophene can be recycled after use. The C-H amidation was shown to proceed with high selectivity and gave the mono-amidated products, mostly in good to excellent yields.

Trans Influence of Ligands on the Oxidation of Gold(I) Complexes.

Gold(I) complexes are considered active species toward oxidative addition; current understanding indicates a different mechanism in contrast to other late transition metals, but a rational understanding of the reactivity profile is lacking. Herein, we propose that the accessibility of the gold(I) center to tri- or tetra-coordination is critical in the oxidative process involving a tri- or tetra-coordinate gold(I) with the oxidizing reagent as one of the ligands as an intermediate. A computational study of the geometry of (Phen)R3PAu(I)NTf2 complexes shows that the accessibility of such tricoordinate species shows a good correlation with the "trans influence" of phosphine ligands: the weak σ-donating phosphine ligands promote tricoordination of gold(I) complexes. The oxidative addition to the asymmetric tricoordinate (Phen)R3PAu(I)NTf2 complexes with alkynyl hypervalent iodine reagents was built. The kinetic profile of the oxidative addition exhibits a good relationship to the Hammett substituent parameter (ρ = 3.75, R2 = 0.934), in which the gold(I) complexes bearing less σ-donating phosphine ligands increase the rate of oxidative addition. The positive ρ indicates a high sensitivity of the oxidative addition to the trans influence. The reactivity profile of oxidative addition to a linear bis(pyridine)gold(I) complex further supports that the oxidative addition to gold(I) complexes is promoted by ligands with small trans influence.

1,1-Digoldallylium Complexes: Diaurated Allylic Carbocations Indicate New Prospects of the Coordination Chemistry of Carbon.

Reacting (NHC)(cyclopropenyl)gold(I) complexes with cationic gold complexes [(IPr)AuX] afforded extremely reactive allylium-1,1-diido-bridged digold intermediates. We prove the existence and constitution of this structure with FT-ICR-MS/MS, NMR, and UV-vis-NIR experiments and isolated the nucleophilic addition product [(Me)(Ph)(CCHC){Au(IPr)}2(SOMe2)]NTf2 with DMSO. Our computational investigation unveiled that the bonding situation of this µ-allylium-1,1-diido digold domain was best described as a three-center-four-electron bond with a π-backbond. The valence orbitals showed extreme delocalization and strong π-interactions between the three centers Au1-C1-Au2. The bridging carbon atom C1 was best described as trigonal planar sp-hybridized carbon in this structure. Excitation succeeded in UV-vis-NIR measurements with energies as low as near-IR radiation.

Dual Gold/Silver Catalysis Involving Alkynylgold(III) Intermediates Formed by Oxidative Addition and Silver-Catalyzed C-H Activation for the Direct Alkynylation of Cyclopropenes.

While gold-mediated synergistic catalytic processes involving transmetalations with other metals are well understood, AuI /AuIII cycles in these reactions are rarely reported. Herein a gold-catalyzed direct alkynylation of cyclopropenes is enabled by two operating catalytic cycles, an oxidative catalytic cycle involving an alkynyl AuIII complex formed by oxidative addition and one involving a silver-mediated C-H activation.

Highly Strained Organogold Complexes and Their Gold- or Rhodium-Catalyzed Isomerizations.

The synthesis and characterization of (NHC)(tricyclo[4.1.0.02,7 ]hept-1-yl)gold(I) compounds is reported. Several of these organometallic compounds could be obtained by transmetalation from the organolithium precursor to the corresponding (NHC)gold(I) chlorides. These are by far the most strained stable organogold compounds reported so far. With these new compounds we were able to efficiently and selectively accomplish the first gold-catalyzed rearrangement of organogold compounds, even better yields were obtained by the first rhodium-catalyzed rearrangement of these organogold species. (E/Z)-Mixtures of (NHC)(cyclohex-2-en-1-ylidenemethyl)gold(I) were obtained, none of the other known rearrangement products of tricycloheptanes. Additional insight into the chemical and physical properties of the strained compounds was obtained by spectroscopic and computational studies.