Copper-catalyzed deborodeuteration of arylboronic acids/borates using DO as the deuterium source.

A straightforward copper-catalyzed deborodeuteration of arylboronic acids and borates was achieved, employing the cost-effective deuterium source DO. This protocol demonstrates wide substrate applicability, exceptional deuterium incorporation efficiency, and favorable tolerance for various functional groups. Therefore, this approach offers a mild option for further applications in valuable deuterium molecule synthesis.

Rhodium-catalyzed intramolecular cyclization for synthesizing thiodihydropyrans.

Addressing the challenge of constructing multi-substituted dihydropyrans, we present an efficient synthesis method for oxygen-containing heterocycles. Using thiones and metal carbenes, we employed xanthate and triazole to intramolecularly synthesize dihydropyran or dihydrofuran compounds. 1,2-Hydride migration was inhibited, and thiodihydropyrans were obtained in excellent yields.

Aerobic Oxysulfonylation of Olefins Using -Sulfonylaminophthalimides as Sulfonyl Radical Precursors.

Readily accessible -sulfonylaminophthalimides were developed to be efficient sulfonyl radical precursors upon being treated with a base/oxidant under mild conditions. The method was applied to the oxysulfonylation of olefins, providing β-ketosulfones and isobenzofurans stereoselectively. On the basis of control experiments, density functional theory calculations, and the literature, a plausible radical mechanism was proposed.

Copper-Catalyzed Synthesis of Furan-Tethered Benzocyclobutenes via Carbene-Mediated 1,4-Sulfinate Migration-Annulation.

A copper-catalyzed intramolecular cascade reaction of conjugated enynones has been achieved via a pivotal 1,4-sulfinate migration step. This process leverages a cost-effective and ecofriendly copper salt as catalyst, enabling the efficient construction of five- and four-membered rings in a rapid, sequential manner, producing furan-tethered benzocyclobutenes in good to excellent yields under mild conditions. The reaction is characterized by 100% atom economy, outstanding efficiency, and excellent diastereoselectivity in the cases studied.

Fe-TiO/TiO S-scheme homojunction for efficient photocatalytic CO reduction.

CO-to-high value-added chemicals via a photocatalytic route is of interest but strangled by the low efficiency. Herein, a novel Fe-TiO/TiO S-scheme homojunction was designed and constructed by using a facile surface modification approach whereby oxygen vacancy (OV) and Fe introducing on the TiO nanorod surface. The as-synthesized Fe-TiO/TiO S-scheme homojunction exhibits positive properties on promoting photocatalytic CO reduction: i) the nanorod structure provides numerous active sites and a radical charge transfer path; ii) the doped Fe and OV not only synergistically enhance light utilization but also promote CO adsorption; iii) the Fe-TiO/TiO S-scheme homojunction benefits photoexcited charge separation and retains stronger redox capacity.

Synthesis of 3-aminoquinolines from α-imino rhodium carbenes and 2-aminobenzaldehydes.

A facile and efficient synthetic method for 3-aminoquinolines has been reported. The straightforward process starts from easily available triazoles and 2-aminobenzaldehydes. Low catalyst loading and good functional group compatibility are the other two merits of this transformation.

Synthesis of Piperidin-4-one Derivatives via α-Imino Rhodium Carbene-Initiated 1,2-Aryl/Alkyl Migration and Annulation.

Valuable piperidin-4-one derivatives were synthesized in excellent yields via an α-imino carbene-initiated cascade reaction involving 1,2-aryl/alkyl migration and annulation. The excellent selectivity of alkyl migration was attributed to the neighboring group participation of 2-bromoethyl. Features such as high efficiency, excellent migrating selectivity, broad substrate scope, and convenient one-pot procedure qualified this protocol as an effective tool for piperidine derivative synthesis.

Synthesis of dihydropyrroles from -generated zwitterions Rh(adc)/TBAI dual catalysis.

Triggered by formation of α-imino carbene, the regioselective synthesis of dihydropyrroles was achieved a cascade 1,3-sulfinate migration/annulation. The sulfinate group was converted into sulfone during the group migration, and a stable anion bearing two electron-withdrawing groups was thus formed. The addition of a catalytic amount of iodide is believed to assist the cleavage of the C-O bond, and the formation of a more stable carbocation.

Synthesis of Azepane Derivatives via Formal 1,3-Migration of Hydroxy and Acyloxy Groups and Selective Annulation.

Formal 1,3-migration of hydroxy and acyloxy groups initiated by α-imino rhodium carbene was achieved, and the following selective annulations of the corresponding zwitterions could efficiently afford azepane derivatives. Benefiting from a time-saving procedure as well as a good functional group tolerance, this unique migration-annulation protocol could provide an efficient tool for synthesizing seven-membered -heterocycles. The plausible mechanism is discussed.

Synthesis of α-Amino Cyclobutanones via Formal 1,3-Hydroxy Migration Triggered by Formation of α-Imino Rhodium Carbene.

Formal intramolecular 1,3-OH migration of α-imino carbene was achieved producing a unique zwitterion, and the subsequent selective annulation afforded α-amino cyclobutanone. Features such as readily available substrates, mild reaction conditions, a time-saving procedure, excellent functional group compatibility, and valuable transformations of the products qualified this unique protocol as an efficient tool for the synthesis of strained cyclic compounds. Density functional theory calculations were in good agreement with experimental observations, and a plausible mechanism is presented.

Access to tetrahydrocarbazoles and pyrrolo[3,4-]carbazoles through sequential reactions of triazoles and indoles.

Tetrahydrocarbazoles and pyrrolo[3,4-]carbazoles could be synthesized conveniently through sequential reactions of ester-tethered 1-sulfonyl-1,2,3-triazoles and indoles. The reaction conditions were mild and the procedures were quite simple. Moreover, the key intermediate α,β-unsaturated imine acted as a [2C] synthon in the [4 + 2] cycloaddition reaction, and the imino group could be used as a nucleophile to construct the fourth ring.

Synthesis of benzothiazonine by rhodium-catalyzed denitrogenative transannulation of 1-sulfonyl-1,2,3-triazole and thiochromone.

A facile synthesis of multi-functionalized benzothiazonine was achieved by the rhodium-catalyzed denitrogenative annulation of 1-sulfonyl-1,2,3-triazole and thiochromone. In view of the excellent atom economy, broad substrate scope and easy availability of starting materials, the protocol provided an efficient strategy for the construction of medium N,S-heterocycles.

Synthesis of Cyclopropanes via 1,3-Migration of Acyloxy Groups Triggered by Formation of α-Imino Rhodium Carbenes.

A novel and highly efficient synthetic approach to cyclopropanes was realized via 1,3-migration of acyloxy groups triggered by α-imino rhodium carbenes. Excellent chemoselectivity ensured broad compatibility of common functional groups. Merits such as readily available substrates, mild reaction conditions, and time-saving processes qualified this transformation as an attractive alternative strategy to synthesize multifunctionalized cyclopropanes.

From Oxygen to Sulfur and Back: Difluoro -H-phosphinothioates as a Turning Point in the Preparation of Difluorinated Phosphinates: Application to the Synthesis of Modified Dinucleotides.

A simple, two-step procedure to convert α,α-difluorinated H-phosphinic acids into the corresponding H-phosphinothioates is described. The usefulness of these species is demonstrated by their transformation into difluorinated phosphinothioyl radicals and their addition onto alkenes. Additionally, sequential treatment of H-phosphinothioates by a strong base and a primary alkyl iodide constitutes an alternate route to the formation of the C-P bond.

Metal-free synthesis of imidazole by BF·EtO promoted denitrogenative transannulation of N-sulfonyl-1,2,3-triazole.

BF·EtO promoted metal-free denitrogenative transannulation of N-sulfonyl-1,2,3-triazole was reported. Rather than transition metals, BF·EtO was employed for the first time to promote the formation of α-diazoimines from N-sulfonyl-1,2,3-triazoles in nitriles, leading to the synthesis of various imidazoles. The protocol tolerates a broad range of functional groups and could also be applied to the late-stage modification of bioactive molecules, demonstrating the potential of this protocol in organic synthesis.

Metal-Free Synthesis of (E)-Monofluoroenamine from 1-Sulfonyl-1,2,3-triazole and EtO·BF via Stereospecific Fluorination of α-Diazoimine.

A general, stereospecific, and straightforward method for the rapid preparation of functionalized (E)-monofluoroenamines is reported. Rather than transition metals (Rh, Ni, Pd, Cu, Ag, etc.), EtO·BF was employed to promote the formation of α-diazoimine through the Dimroth equilibrium of common 1-sulfonyl-1,2,3-triazole for the first time.

[Analysis of Early-Death and Factors Affecting Prognosis of Patients with Acute Promyelocytic Leukemia].

Objective: To investigate the factors affecting the early-death, overall survival (OS) and relapse-free survival (RFS) of acute promyelocytic leukemia (APL) patients.

Methods: The clinical and laboratorial charachteristics of 176 APL patients in our center were analyzed retrospectively during January 2002 to Mar 2016. The risk factors of early death and factors affecting OS and RFS of patients were analyzed.

Rhodium-catalyzed synthesis of 1,2-dihydropyridine by a tandem reaction of 4-(1-acetoxyallyl)-1-sulfonyl-1,2,3-triazole.

A tandem reaction of 4-(1-acetoxyallyl)-1-sulfonyl-1,2,3-triazole including formation of α-imino rhodium carbene, 1,2-migration of an acetoxy group and six electron electrocyclic ring closure was reported. The migration of the OAc group with excellent chemoselectivity was the crucial process, leading to the formation of 1,2-dihydropyridine specifically in up to 90% yield. Several transformations of the dihydropyridine product were also achieved illustrating the potential of the protocol in organic synthesis.

Metal-free synthesis of 2-aminonaphthalenes by intramolecular transannulation of 1-sulfonyl-4-(2-alkenylphenyl)-1,2,3-triazoles.

A facile metal-free synthesis of naphthalenes by intramolecular transannulation of 1-sulfonyl-4-(2-alkenylphenyl)-1,2,3-triazoles was realized. The in situ formed ketenimine was proposed as the key intermediate, and the desired 2-aminonaphthalenes were generated in up to 87% yield in refluxing 1,2-dichloroethane without any catalyst or additive.

Synthesis of Multifunctionalized 2-Carbonylpyrrole by Rhodium-Catalyzed Transannulation of 1-Sulfonyl-1,2,3-triazole with β-Diketone.

A facile rhodium-catalyzed transannulation of 1-sulfonyl-1,2,3-triazoles with β-diketones was realized, and a series of multisubstituted 2-carbonylpyrroles were synthesized efficiently (up to 94% yield). The protocol features several advantages, such as readily available materials, mild reaction conditions, a concise operating procedure, a broad reaction scope, and excellent regioselectivity when benzoylacetone derivatives were used.

Long-term outcomes of imatinib in patients with FIP1L1/ PDGFRA associated chronic eosinophilic leukemia: experience of a single center in China.

Background: The FIP1L1/PDGFRA (F/P) fusion gene is the most common clonal genetic abnormality of chronic eosinophilic leukemia (CEL). Tyrosine kinase inhibitors (TKI), such as imatinib, have been demonstrated to be effective therapies for F/P mutated disease. The aim of this study was to analyze the treatment response and long term prognosis in patients with F/P mutated CEL.

Standardized fluorescence in situ hybridization testing based on an appropriate panel of probes more effectively identifies common cytogenetic abnormalities in myelodysplastic syndromes than conventional cytogenetic analysis: a multicenter prospective study of 2302 patients in China.

In an attempt to establish the advantages of fluorescence in situ hybridization (FISH) studies over conventional cytogenetic (CC) analysis, a total of 2302 de novo MDS patients from 31 Chinese institutions were prospectively selected in the present study for both CC and standardized FISH analysis for +8, -7/7q-, -5/5q-, 20q- and-Y chromosomal abnormalities. CC analysis was successful in 94.0% of the patients; of these patients, 35.

Copper-catalyzed regio- and stereoselective O-arylation of enolates.

Copper-catalyzed O-arylation of enolates with diaryliodonium salts as arylating reagents was realized successfully. As important building blocks, β-aryloxy carbonyl compounds were obtained in up to 98% yield under mild conditions, and complete control of O-arylation and Z-stereoselectivity were achieved. The origin of the selectivity was also discussed.