Enhanced spectral resolution in mid-infrared dual-comb spectroscopy via synchronous offset frequency tuning.

Mid-infrared dual-comb spectroscopy offers significant advantages by combining the high sensitivity of mid-infrared spectroscopy with the high spectral resolution and rapid acquisition of the dual-comb method. However, its effective resolution, constrained by the inherent comb line spacing, hinders its ability to resolve narrow absorption features, common in critical applications such as sub-Doppler spectroscopy, low-pressure gas analysis, and construction of the atmospheric profile. To address this challenge, we present a synchronous offset frequency tuning method for the mid-infrared dual-comb system to improve effective resolution far beyond comb line spacing.

Synthesis of β,β-Dithioketones by Merging C-C and C-S Bond Cleavage in [1 + 1 + 1 + 1 + 1 + 1] Annulation.

An unconventional [1 + 1 + 1 + 1 + 1 + 1] annulation process was developed for the construction of β,β-dithioketones by merging C-C and C-S bond cleavage. In this reaction, rongalite concurrently served as triple C1 units, dual sulfur(II) synthons, and a reductant for the first time. Mechanism investigation indicated that the reaction involved the self-mediated valence state change of rongalite.

Direct Hydrodefluorination of CF-Alkenes via a Mild S2' Process Using Rongalite as a Masked Proton Reagent.

A concise and efficient hydrodefluorination process was developed for the synthesis of -difluoroalkenes. This reaction employs rongalite as a masked proton source and does not require any additional catalysts or reductants. Notably, trifluoromethyl alkenes having both terminal and internal double bonds are compatible with this process, allowing for a wider range of substrates.

A Pummerer Reaction-Enabled Modular Synthesis of Alkyl Quinoline-3-carboxylates and 3-Arylquinolines from Amino Acids.

Concise synthesis of functionalized quinolines has received continuous research attention owing to the biological importance and synthetic potential of bicyclic -heterocycles. However, synthetic routes to the 2,4-unsubstituted alkyl quinoline-3-carboxylate scaffold, which is an important motif in drug design, remain surprisingly limited, with modular protocols that proceed from readily available materials being even more so. We herein report an acidic I-DMSO system that converts readily available aspartates and anilines into alkyl quinoline-3-carboxylate.

Synthesis of Tetrahydro-2-thiopyran 1,1-Dioxides via [1+1+1+1+1+1] Annulation: An Unconventional Usage of a Tethered C-S Synthon.

An unprecedented [1+1+1+1+1+1] annulation process has been developed for the construction of tetrahydro-2-thiopyran 1,1-dioxides. Notably, rongalite acted as a tethered C-S synthon in this reaction and can be chemoselectively used as triple C1 units and as a source of sulfone. Mechanistic investigation indicated that two different carbon-increasing models are involved in this reaction in which rongalite serves as C1 units.

Pd-Catalyzed Hydroxyl-Directed Cascade Hydroarylation/C-H Germylation of Nonterminal Alkenes and Aryl Iodides.

Pd-catalyzed cascade hydroarylation and C-H germylation of nonterminal alkenes and aryl iodides enabled by hydroxyl assistance have been developed. The key step in this C-H germylation cascade is the formation of a highly reactive oxo-palladacycle intermediate, which markedly restrained the β-H elimination process. Mechanistically, control experiments indicated that the hydroxyl group played an important role in this process.

Access to 2-arylquinazolines catabolism/reconstruction of amino acids with the insertion of dimethyl sulfoxide.

Quinazoline skeletons are synthesized by amino acid catabolism/reconstruction combined with the insertion/cyclization of dimethyl sulfoxide for the first time. The amino acid acts as a carbon and nitrogen source through HI-mediated catabolism and is then reconstructed using aromatic amines and dimethyl sulfoxide (DMSO) as a one-carbon synthon. This protocol is of great significance for the further study of the conversion of amino acids.

Palladium catalyzed annulation of 2-iodobiphenyl with a non-terminal alkene enabled by neighboring group assistance.

In this work, an efficient palladium catalyzed annulation of 2-iodobiphenyl with a non-terminal alkene was developed. The key factor in this transformation was the formation of a highly reactive oxo-palladacycle intermediate, which was enabled by a neighboring hydroxyl group, and remarkably restrained the β-H elimination process. Mechanistically, control experiments demonstrated that the hydroxyl group may act as an anionic ligand, which was irreplaceable in this reaction.

Quadruple C-H activation coupled to hydrofunctionalization and C-H silylation/borylation enabled by weakly coordinated palladium catalyst.

Unlike the well-reported 1,2-difunctionalization of alkenes that is directed by classic pyridine and imine-containing directing groups, oxo-palladacycle intermediates featuring weak Pd-O coordination have been less demonstrated in C-H activated cascade transformations. Here we report a quadruple C-H activation cascade as well as hydro-functionalization, C-H silylation/borylation sequence based on weakly coordinated palladium catalyst. The hydroxyl group modulates the intrinsic direction of the Heck reaction, and then acts as an interrupter that biases the reaction away from the classic β-H elimination and toward C-H functionalization.

Rongalite as a sulfone source: a novel copper-catalyzed sulfur dioxide anion incorporation process.

A novel copper-catalyzed sulfur dioxide anion incorporation cascade for the synthesis of 1-thiaflavanone sulfones has been disclosed using rongalite as an economic and safe sulfone source. A series of 1-thiaflavanone sulfones were synthesized from easily prepared 2'-iodochalcone derivatives in excellent yields. This transformation proceeds through consecutive formation of two C-S bonds, which is the first example of SO being used to construct sulfone motifs under copper-catalyzed conditions.

Aryldiazonium Salts Serve as a Dual Synthon: Construction of Fully Substituted Pyrazoles via Rongalite-Mediated Three-Component Radical Annulation Reaction.

A highly efficient rongalite-mediated three-component radical annulation reaction to furnish fully substituted pyrazoles from aryldiazonium salts and α,β-unsaturated aldehydes or ketones under metal- and oxidant-free conditions at room temperature has been developed. In this transformation, aryldiazonium salts served as the precursor of both the aryl and aryl hydrazine units. Mechanistic investigations indicated that rongalite could act as a radical initiator and reducing reagent simultaneously in the reaction.

I/DMSO-mediated multicomponent reaction of o-hydroxyaryl methyl ketones, rongalite, and DMSO: access to C3-sulfenylated chromones.

An efficient I2-DMSO reagent system-mediated multicomponent reaction strategy for the synthesis of C3-sulfenylated chromones from o-hydroxyaryl methyl ketones, rongalite, and dimethyl sulfoxide has been developed. Notably, the double C-S bond cleavages of rongalite and dimethyl sulfoxide served as key steps in this smooth transformation, affording the C1 unit and sulfur source for the assembly of C3-sulfenylated chromones. Preliminary mechanistic studies indicated that in situ generated HCHO and (2-(2-hydroxyphenyl)-2-oxoethyl)dimethylsulfonium iodine were probably the key intermediates in this transformation.

The triple role of rongalite in aminosulfonylation of aryldiazonium tetrafluoroborates: synthesis of N-aminosulfonamides via a radical coupling reaction.

A simple and convenient method for N-aminosulfonamide synthesis from the cross-coupling of aryldiazonium tetrafluoroborates and rongalite under metal-free, oxidant-free, and room-temperature conditions is reported. This method does not require an external amine source, with the aryldiazonium tetrafluoroborates participating as both an aryl radical and a potential amine source in the transformation. Mechanistic studies revealed that rongalite could act as a radical initiator, a sulfur dioxide surrogate and a reducing reagent simultaneously in this reaction.

C(sp)-H Bond Functionalization of Benzo[ c]oxepines via C-O bond Cleavage: Formal [3+3] Synthesis of Multisubstituted Chromans.

An efficient base-promoted C(sp)-H bond functionalization strategy for the synthesis of multisubstituted chromans from the formal [3+3] cycloaddition of benzo[ c]oxepines and electron-rich phenols has been developed. The corresponding 4 H-chromenes can be easily obtained in excellent yields by simple filtration from chromans. Preliminary mechanistic studies indicate that the C-O bond cleavage is the key step for the C(sp)-H bond functionalization and that this reaction could have occurred through tandem C-O bond cleavage/Michael addition/annulation reactions.

A C-H Oxidation/Two-Fold Cyclization Approach to Imidazopyridoindole Scaffold under Mild Oxidizing Conditions.

An expeditious one-step synthesis of the imidazopyridoindole scaffold was achieved through the C-H oxidation/two-fold cyclization reaction of methyl ketone and tryptamine derivatives. Mild oxidizing conditions were employed to realize the efficient oxidation of C(sp)-H bonds, while suppressing overoxidation of the intermediate and ensuring the cross-trapping of two in situ generated acylimine intermediates.

Divergent Synthesis of Functionalized Quinolines from Aniline and Two Distinct Amino Acids.

A practicable quinoline synthesis from aniline and two amino acids was developed for generating a wide range of quinolines with high efficiency and diversity. Thus, it facilitated the creations of pharmaceutical derivatives, photochemical active compounds, and challenging scaffolds. The concept of using two amino acids as heterocyclic precursors has been raised for the first time.

Oxidative Trimerization of Amino Acids: Selective Synthesis of 2,3,5-Trisubstituted Pyridines.

An oxidative trimerization of three amino acids has been realized to furnish 2,3,5-trisubstuitued pyridines in both cross- and homo-trimerization types. This method is capable of converting simple linear biomass material to heterocycles, which features in the assembly of three amino acid branched chains into one aromatic ring. Molecular iodine triggers the sequential decarboxylation and deamination of amino acids and then promotes the selective formation of new C-N and C-C bonds.