4-Aryl-3-thiocyanatobutan-2-ones were prepared by Meerwein reactions from methyl vinyl ketone and aryldiazonium salts under copper(II) catalysis in 35–75% yields. α-Thiocyanato ketones regioselectively react with 1-methyl-3-aminopyrazole forming N-(3-pyrazolyl)-substituted 2-aminothiazoles in 80–91% yields. An ester group in position 3 of the pyrazole induced a regioselective ring-closure reaction

The affiliation of the corresponding author Xiaojie Lu was incorrect. Previously published affiliation: State Key Laboratory of Drug Research, Shanghai Institute of Materia Medica, Chinese Academy of Sciences, 501 Haike Road, Zhang Jiang Hi-Tech Park, Pudong, Shang-hai, 201203, China Corrected affiliation: State Key Laboratory of Drug Research, Shanghai Institute of Materia Medica, Chinese Academy

We report the synthesis of iminosugar C,C-glycosides starting from 6-azidoketopyranoses. Their Staudinger-azaWittig-mediated cyclization provided bicyclic N,O-acetals, which were stereoselectively opened with AllMgBr to afford β-hydroxyazepanes with a quaternary carbon α to the nitrogen. Their ring contraction via a β-aminoalcohol rearrangement produced the six-membered l-iminosugars with two functional

Palladium-catalyzed regioselective [5 + 1] annulation reactions of vinyl aziridines/epoxides with ClCF2COONa have been developed. Significantly, vinyl aziridines/epoxides act as heteroatom-containing five-atom synthons, and commercially available and cheap ClCF2COONa acts as the source of carbonyl serving as a difluorocarbene precursor. This protocol provides an efficient and practical method for the

Boron/nitrogen-doped fluoranthenes, a new class of BN-doped cyclopenta-fused polycyclic aromatic hydrocarbons, were synthesized via pyrrolic-type nitrogen directed C–H borylation. Regioselective bromination of BN-fluoranthene (3a) gave mono- and dibrominated BN-fluoranthenes. The halogenated BN-fluoranthene (3b) can undergo various of further cross-coupling reactions to deliver a series of BN-fluoranthenes

Differentiation of heterocyclic isomers by solution 1H, 13C, and 15N NMR spectroscopy is often challenging due to similarities in their spectroscopic signatures. Here, 13C{14N} solid-state NMR spectroscopy experiments are shown to operate as an “attached nitrogen test”, where heterocyclic isomers are easy to distinguish based on one-dimensional nitrogen-filtered 13C solid-state NMR. We anticipate that

A new class of tailor-made push–pull isoindole fluorophores has been synthesized through the combination of Suzuki coupling and Knoevenagel reactions. The efficient synthetic strategy rendered the isoindole scaffold as the π-bridge and the isolation spacer and provided dyes bearing various types of electron donors and electron acceptors for manipulating their energy gaps and tuning their absorptions

N-Polyheterocycles are rapidly accessed by N-heterocyclic carbene (NHC) catalysis through regioselective sequential radical addition/cyclization in the absence of any metals or oxidants. The transformation occurs under mild conditions and enjoys a wide substrate scope with excellent functional group compatibility. Furthermore, a gram-scale synthesis is also conducted. Preliminary mechanistic studies

By utilizing an underexplored reaction mode of C,N-cyclic azomethine imines, a catalyst-free [1+2+3] cycloaddition/N–N bond cleavage sequential reaction for accessing spiroindolines with syn-stereoselectivity was developed. On the basis of experimental results and DFT calculations, peroxide and ethereal solvent were identified to trigger the hydrogen abstraction of the unstable [1+2+3] cycloaddition

A highly efficient rhodium-catalyzed formal C–H insertion reaction between indoles and 1-diazonaphthoquinones has been established, providing a novel protocol for the atroposelective synthesis of axially chiral C2-arylindoles (up to 99:1 er) under mild reaction conditions. Typically, only 1 mol % of Rh2(S-PTTL)4 is used and the chelation group is not needed for this conversion.

Herein, a practical and highly efficient method for visible-light-induced copper-catalyzed N-aminoquinoline-directed asymmetric C(sp3)–C(sp3)–H glycosylation was reported. At the same time, C(sp3)–C(sp3)–H glycosylation of nondeoxysugars with amino acids to construct C-glycopeptides was achieved. This approach promoted the synthesis of various C-glycopeptides and provided a new model for the synthesis

Methods for site-selective sulfamoylation of secondary hydroxyl groups in pyranosides are described. Using a boronic acid catalyst, selective installation of a Boc-protected sulfamoyl group at the equatorial position of cis-diols in manno- and galacto-configured substrates has been achieved. Activation of trans-diol groups in gluco- and galacto-configured substrates is also possible by employing an

A photoinduced, iron(III) chloride-catalyzed C–H activation of N-methyl amides and ethers leads to the formation of C–S and C–Se bonds via a ligand-to-metal charge transfer (LMCT) process. This methodology converts secondary and tertiary amides, sulfonamides, and carbamates into the corresponding amido-N,S-acetal derivatives in good yields. Mechanistic work revealed that this transformation proceeds

The development of stoichiometric oxidant-free regioselective annulation protocol is a challenging aspect in organic synthesis. Herein, we disclose electricity as a greener oxidant for the C–H/N–H annulation to construct cinnolines using rhodium(III) catalyst under mild conditions. A detailed mechanistic investigation revealed the possibility of both Rh(III/I) and Rh(III/IV) catalytic cycles for the

A cobalt-catalyzed multipositional isomerization of conjugated dienes has been reported for the first time using an 8-oxazoline iminoquinoline ligand. This reaction is operationally simple and atom-economical using readily available starting materials with an E/Z mixture to access disubstituted 1,3-dienes with excellent yields and good E,E stereoselectivity. The mechanism via alkene insertion of cobalt

A photoinduced, photocatalyst-free cyanoalkylation of nitrostyenes was explored, affording a series of cyanoalkylated alkenes in moderate to good yields. Mechanistic studies reveal that an electron donor–acceptor complex formed between O-aryl oximes and DIPEA is presumably involved in this process. The excellent functional group compatibility of this newly designed synthetic protocol allows for cyanoalkylation

An electrochemical synthesis of diazo compounds from hydrazones in yields as high as 99% was performed. This method was elaborated as a useful synthetic method and demonstrated on various diazo compounds (24 examples). Apart from exhibiting an efficiency that matched that of commonly used harsh and toxic chemical oxidants, this reaction is practically simple to set up, requires mild conditions, and

Developed herein is an enantioselective Friedel–Crafts alkylation reaction of N-unprotected alkynyl trifluoromethyl ketimines with pyrroles catalyzed by chiral phosphoric acid to furnish chiral primary α-trifluoromethyl-α-(2-pyrrolyl)propargylamines with high enantioselectivity. Transformation of the alkynyl group of the adducts afforded optically active α-trifluoromethylated amines bearing various

An aminooxy click chemistry (AOCC) strategy was used to synthesize nucleoside building blocks for incorporation during solid-support synthesis of oligonucleotides to enable bis-homo and bis-hetero conjugation of various biologically relevant ligands. The bis-homo aminooxy conjugation leads to bivalent ligand presentation, whereas the bis-hetero conjugation allows the placement of different ligands

A synthetic approach toward densely substituted enantiopure cyclic sulfinamides possessing up to four consecutive stereogenic centers was developed based on a completely diastereoselective SN2′ cyclization/tert-Bu cleavage sequence. Diastereospecific transformation of the obtained scaffold into chiral SVI derivatives such as sulfoximines and sulfonimidamides is demonstrated.

The structure of 2l in Scheme 4 has been misassigned and it should be drawn as follows: The structure 2l on page S20 of the Supporting Information should also be drawn as above. The name should be replaced with 2-Methyl-2,5,6,7,8,9-hexahydro-1H-benzo[c]azepin-1-one (2l) The spectroscopic data in the Supporting Information are correct, and this finding does not impact on the conclusions of the paper

Electrosynthesis is effectively employed in a general regio- and stereoselective alkylation of Morita–Baylis–Hillman compounds. The exposition of N-acyloxyphthalimides (redox-active esters) to galvanostatic electroreductive conditions, following the sacrificial-anode strategy, is proved an efficient and practical method to access densely functionalized cinnamate and oxindole derivatives. High yields