ACS Organic & Inorganic Au最新文献

Isoquinoline-1,3-(2H,4H)-diones have been the subject of numerous studies toward new pharmaceuticals, and therefore novel, mild functionalizations of this scaffold are highly desirable. As diazo compounds are versatile reagents in organic synthesis, 4-diazoisoquinoline-1,3-(2H,4H)-diones should give access to a broad range of various derivatives. Indeed, they enable the introduction of fluorinated moieties via photochemical O-H insertion reactions in serviceable yields, typically in under 2 h. Exchanging the 1-carbonyl group with the sulfoxide moiety causes a hypsochromic shift in the absorption of the diazo compounds, and thus, violet light is required for effective O-H and S-H insertion reactions.

Nitrogen heterocycles and aromatic amines are well-known and widely used compounds that are usually not seen as acids, although in organic solvents like acetonitrile (MeCN) or dimethyl sulfoxide (DMSO) their acidic properties can be observed. In this work, the acidities (pK _a values) of 37 such weak NH acids were determined in acetonitrile and presented together with computational gas-phase acidities and literature pK _a values in DMSO. In the course of the work the weakest acids range (from pK _a 29 upward) of the MeCN acidity scale has been revised and expanded to around 33.5 by adding 31 compounds in that specific region and the span of experimental pK _a values in MeCN is now more than 30 orders of magnitude. The relations between the structure and acidity of a selection of the studied compounds have been investigated in MeCN and DMSO. The measured pK _a values in MeCN and the gathered pK _a values in DMSO were used for a correlation analysis between the two solvents and for assessing the quality of pK _a conversion equations. A number of pK _a values have been predicted in MeCN from pK _a values in DMSO via the correlation analysis and pK _a conversion equations.

The present study employs DFT calculations and the independent gradient model (IGM) approach to investigate a mechanism study of the hydroboration reaction of internal alkynes catalyzed by Ag-(I)-IMes and Cu-(I)-IMes complexes. A detailed analysis of the mechanism's steps revealed that Cu-(I)-IMes exhibits superior efficiency, showing a more favorable energy pathway than Ag-(I)-IMes. The IGM method was crucial for quantifying molecular interactions, highlighting essential differences in binding forces between catalysts and substrates throughout the catalytic steps. For Cu-(I)-IMes, the migratory insertion step (TS1) demonstrated a barrier 2.5 times lower than its Ag-(I)-IMes counterpart. Additionally, the protonation step (TS2) exhibited lower energy for Cu-(I)-IMes compared to Ag-(I)-IMes, indicating a more efficient formation of the desired β-product. The results also suggest that Cu-(I)-IMes operates on a more efficient pathway, with lower energy for the catalytic cycle. These findings, coupled with detailed analyses of molecular interactions using the IGM method, provide an enhanced understanding of the reaction mechanism, highlighting the promising efficacy of Cu-(I)-IMes as a catalyst in hydroboration reactions.

Metal halide semiconductors (MHS) are a versatile class of materials with fully customizable mechanical and optoelectronic properties that have proven to be prominent candidates in numerous impactful applications. Finding a way to generate porosity in MHS would bestow upon them an additional node in property engineering, thus allowing them to be utilized in uncharted technologies. Motivated by this promise, we developed a general strategy to render the MHS porous. We employed molecular cages as structure-directing agents and countercations, which fostered a new family of materials: porous metal halide semiconductors (PMHS). The presence of molecular cages gave rise to ultramicroporous structures imposed by the organic part cavities and a record water stability performance of 27 months so far. In this Perspective, we discuss the principles and promises of PMHS, which combine the merits of porous and electronic compounds.

Practical and atom-economic procedures for the selective synthesis of HFIP ester-containing indenes/thiochromenes from the same propargylic thioethers and HFIP have been developed via one-pot NIS-promoted cyclization/palladium-catalyzed carbonylation. Solvent plays an important role in this transformation, and the reactions proceed selectively and efficiently to afford a variety of HFIP ester-containing indenes and thiochromenes in moderate to excellent yields. In addition, the use of formic acid as the CO source could avoid manipulation of toxic CO gas.