Water can accelerate a variety of organic reactions far beyond the rates observed in classical solvents. However, using pure water as solvent introduces solubility constraints that have limited applicability efficient photochemistry particular. We report here formation aggregates between pairs arenes, heteroarenes, enamines, or esters with different electron affinities an aqueous medium, leading to oil-water phase boundary through substrate melting point depression. The active hydrogen atoms...

A highly selective and general photocatalytic C-F borylation protocol that employs a rhodium biphenyl complex as triplet sensitizer the nickel catalyst [Ni(IMes)2] (IMes = 1,3-dimesitylimidazoline-2-ylidene) for bond activation defluoroborylation process is reported. This tandem system operates with visible (blue, 400 nm) light achieves of wide range fluoroarenes B2pin2 at room temperature in excellent yields high selectivity. Direct irradiation intermediary oxidative addition product...

A highly efficient and general protocol for traceless, directed C3-selective C-H borylation of indoles with [Ni(IMes)2] as the catalyst is reported. Activation N-H bonds by essential to install a Bpin moiety at N-position traceless directing group, which enables bonds. The N-Bpin group formed easily converted in situ back an oxidative addition product situ-generated HBpin. catalytic reactions are operationally simple, allowing variety substituted B2pin2 excellent yields high selectivity. can...

A highly selective and general photoinduced C-Cl borylation protocol that employs [Ni(IMes)2] (IMes = 1,3-dimesitylimidazoline-2-ylidene) for the radical of chloroarenes is reported. This system operates with visible light (400 nm) achieves a wide range B2pin2 at room temperature in excellent yields high selectivity, thereby demonstrating its broad utility functional group tolerance. Mechanistic investigations suggest reactions proceed via process. EPR studies demonstrate undergoes very fast...

An unusual multiple isocyanide insertion reaction with methyleneindolinone using indium(III) chloride as the catalyst has been disclosed. This strategy allows for rapid construction of structurally complex spirooxindole in an efficient manner. The present protocol features mild conditions, atom economy, and broad substrate scope.

The amino alcohol meglumine solubilizes organic compounds in water and enforces the formation of electron donor acceptor (EDA) complexes haloarenes with indoles, anilines, anisoles or thiols, which are not observed solvents. UV-A photoinduced transfer within EDA induces mesolytic cleavage halide ion radical recombination arenes leading, after rearomatization proton loss to C-C C-S coupling products. Depending on substitution pattern selective unique cross-couplings observed. UV NMR...

A novel strategy to furnish selective double insertion of isocyanides with the aid potassium tetrachloroaurate(III) has been disclosed. This provides quick access approach a complex polycyclic skeleton in an efficient manner. Unexpected oxygen migration was also observed when reaction conducted at lower temperature.

We report the iridium–nickel dual photocatalytic acceptorless and redox neutral dehydrogenation of aliphatic heterocycles yielding cyclic alkenes without overoxidation at room temperature. Excitation iridium photocatalyst initiates formation a nickel hydride intermediate that yields H2 via β-hydride elimination. The reaction proceeds regioselectively scope was demonstrated by synthesis 12 biologically relevant molecules drugs. In addition, commercially easily available N-heterocyclic alkane...

Postsynthetic diversification of peptides through selective modification endogenous amino acid side chains has enabled significant advances in peptide drug discovery while expanding the biological and medical chemistry space. However, current tools have been focused on reactive polar ionizable chains, whereas decoration aromatic systems (e.g., N(in) tryptophan) a long-standing challenge. Here, we introduce metallaphotocatalysis solid-phase synthesis for on-resin orthogonal N-arylation...

Abstract We report herein a mild procedure for the copper‐catalyzed oxidative cross‐coupling of electron‐deficient polyfluorophenylboronate esters with terminal alkynes. This method displays good functional group tolerance and broad substrate scope, generating cross‐coupled alkynyl(fluoro)arene products in moderate to excellent yields. Thus, it represents simple alternative conventional Sonogashira reaction.

A novel protocol for the transition metal-free 1,2-addition of polyfluoroaryl boronate esters to aldehydes and ketones is reported, which provides secondary alcohols, tertiary ketones. Control experiments DFT calculations indicate that both ortho-F substituents on polyfluorophenyl boronates counterion K+ in carbonate base are critical. The distinguishing features this procedure include employment commercially available starting materials broad scope reaction with a wide variety carbonyl...

We report a simple protocol for the transition metal-free, visible-light-driven conversion of 1,3-diketones to tetra-substituted furan skeleton compounds in carbon dioxide (CO2) atmosphere under mild conditions. It was found that CO2 could be incorporated at diketone enolic OH position, which key enabling cleavage C-O bond during rearrangement cyclopropane intermediate. This method allows same-pot construction two isomers high-value scaffold. The synthetic scope and preliminary mechanistic...

Abstract A switchable oxidative coupling reaction of isocyanide and peroxide has been disclosed. In the presence iron catalyst, affords N‐arylacetamides in good yields. By simply replacing with copper another different takes place which can serve as alkoxylating source. This protocol represents a new fundamental two basic chemicals involving C−C C−O bond‐forming process. The unusual reactivity an isocyano group radical acting formally amidoyl synthon also well established. experiment outcome...

Photoinduced borylation has emerged as a valuable strategy for synthesizing arylboronic esters. However, photochemical transformations involving inert bonds such C(sp2)−F are still challenging. Herein, we report straightforward and operationally simple method the activation of various carbon−heteroatom bonds, enabling synthesis diverse esters without need transition metals or catalysts. Mechanistic investigations reveal that deprotonation DMSO plays pivotal role in reaction, excited anion...

A multicomponent bicyclization of isocyanide, allenoate, imine, and water has been disclosed. This protocol involves the formation five chemical bonds (two C–C, two C–N, one C–O), thus providing a new pathway to fused rings.

Abstract The amino alcohol meglumine solubilizes organic compounds in water and enforces the formation of electron donor acceptor (EDA) complexes haloarenes with indoles, anilines, anisoles or thiols, which are not observed solvents. UV‐A photoinduced transfer within EDA induces mesolytic cleavage halide ion radical recombination arenes leading, after rearomatization proton loss to C−C C−S coupling products. Depending on substitution pattern selective unique cross‐couplings observed. UV NMR...

Abstract A novel protocol for the transition metal‐free 1,2‐addition of polyfluoroaryl boronate esters to aldehydes and ketones is reported, which provides secondary alcohols, tertiary ketones. Control experiments DFT calculations indicate that both ortho‐F substituents on polyfluorophenyl boronates counterion K + in carbonate base are critical. The distinguishing features this procedure include employment commercially available starting materials broad scope reaction with a wide variety...

The article analyses current situation and some critical problems in railway materials purchasing. In order to improve the management, a purchasing management Strategy model about grading classifying is proposed. based on material grouping method provides basis for decisions key such as how divide authority, choose mode of To verify effectiveness model, calculation using data carried out. results show that can provide targeted strategies grouped materials. research ideas fine China Railway...

Abstract The Au‐catalyzed reaction of oxindolylideneacetates (I) with aryl isocyanides (II) in refluxing toluene leads to tricyclic derivatives (III), whilst the at 95°C is accompanied by an oxygen migration afford products (IV).