A chemoselective N-arylation reaction of 2-aminopyridine derivatives with arynes in good to excellent yields has been described. The N-arylation products could be further applied to the facile construction of benzoisoquinuclidines and isoquinuclidines as well as pyrido[1,2-a]benzimidazoles.

An efficient protocol for facile construction of spiro[indazole-3,3′-indolin]-2′-ones was developed via [3 + 2] dipolar cycloaddition of arynes with 3-diazoindolin-2-ones under mild conditions in excellent yields. Subsequent thermal isomerization of the spiro[indazole-3,3′-indolin]-2′-ones readily afforded indazolo[2,3-c]quinazolin-6(5H)-ones.

A novel Pd(II)-catalyzed cascade reaction has been developed that consists of a highly regio- and stereoselective oxa [4 + 2] cycloaddition reaction of o-alkynylbenzaldehydes and an intramolecular carboxylic group quenching of the in situ generated oxonium ion. This new reaction provides a one-step construction of the tetracyclic core structure of chaetophenol C from two simple starting materials. The developed chemistry was successfully applied to the first total synthesis of chaetophenol C and dozens of its analogues.

An asymmetric total synthesis of (−)-aspidophylline A has been accomplished. The key transformations include an asymmetric hydride transfer hydrogenation of an α,β-acetylenic ketone and a cationic gold(I)-catalyzed 6-exo-dig cyclization involving an alkynylindole/aminal formation cascade, which enables stereoselective establishment of the requisite quaternary carbon center.

The tricyclic intermediate 2 has been synthesized in eight steps from known compound 6 in 20% overall yield. As such, this constitutes a highly efficient formal synthesis of (±)-aplykurodinone-1. This synthesis features a unique, one-pot, intramolecular hetero-Pauson-Khand reaction (h-PKR)/desilylation sequence to expeditiously construct the tricyclic framework, providing valuable insights for expanding the scope and boundaries of h-PKR.

Cobaloxime (Co(dmgBF2)2·2H2O), an inexpensive first-row transition-metal complex, catalyzed hydration of terminal alkynes gave the corresponding methyl ketones in good to excellent yields under neutral conditions (additional protic acids and silver salts are not required). A wide range of functional groups, such as allyl ether, benzyl ethers, carboxylic esters, imides, amides, nitro, and halogens, were tolerated. The mild reaction conditions together with the inexpensive feature and easy availability of the catalyst well address the current challenges in the field of alkyne hydration.

A blue-light-promoted carbon–carbon double bond isomerization in the absence of any photoredox catalyst is reported. It provides rapid access to a series of quinolines in good to excellent yields under simple aerobic conditions. The protocol is direct, catalyst-free and operationally convenient.

A new route to arylhydrazides involving the reaction of two highly active intermediates, the 1,3-zwitterion generated in situ from the Mitsunobu reagent and arynes, under mild conditions has been developed. Further transformations of the versatile arylhydrazides to diverse nitrogen-containing heterocycles in one pot are also demonstrated.

A practical method for dehydration of alcohols, mainly propargyl alcohols, promoted by silyl-EBX is reported, which represents the first example of using only a catalytic amount of silyl-EBX since its discovery. A broad range of aryl propargyl alcohols proceeded smoothly and gave the dehydration products in good to excellent yields. Preliminary mechanistic studies ruled out the radical pathways and supported an E1 process for this reaction. The carbon–carbon triple bond and the lactone moiety within the EBX molecule may have played an important role in the reaction.

A route to rare spiro-3H-indazoles bearing a carbonyl group adjacent to the spirocyclic quarternary carbon via 1,3-dipolar cycloaddition reaction of arynes with 6-diazocyclohex-2-en-1-one derivatives under mild conditions has been developed. Further transformation of these unique spiro-3H-indazoles via an acid- or heat-mediated rearrangement to fused-2H-indazoles and an interesting reduction/ring-opening/reduction sequence are also described.

Correction for ‘Decarboxylative Csp3–Csp3 coupling for benzylation of unstable ketone enolates: synthesis of p-(acylethyl)phenols’ by Sasa Wang et al., Chem. Commun., 2016, 52, 9454–9457.

A Rh(II)-catalyzed dearomative intramolecular [3 + 2] dipolar cycloaddition involving the indolic C2–C3 carbon–carbon double bond has been developed. The reaction was launched from the triazole moiety within the substrate and proceeded efficiently under mild conditions. A wide range of functional groups could be tolerated. These features render the current reaction a highly useful tool for the synthesis of polycyclic indole alkaloids, as showcased by a rapid assembly of the core structure of Aspidosperma and the related alkaloids.

A new decarboxylative Csp3–Csp3 coupling approach for the benzylation of ketone enolates has been developed. A variety of raspberry ketone derivatives were conveniently synthesized in good to excellent yields under mild conditions. A crossover reaction shed light on the mechanism of this tandem reaction.

A novel and efficient protocol for the rapid construction of dibenzofuran motifs from 6-diazo-2-cyclohexenone and ortho-haloiodobenzene has been developed. The process involves one-pot Pd-catalyzed cross-coupling/aromatization and Cu-catalyzed Ullmann coupling.

A blue-light-promoted carbon–carbon double bond isomerization in the absence of any photoredox catalyst is reported. It provides rapid access to a series of quinolines in good to excellent yields under simple aerobic conditions. The protocol is direct, catalyst-free and operationally convenient.

Cobaloxime (Co(dmgBF2)2·2H2O), an inexpensive first-row transition-metal complex, catalyzed hydration of terminal alkynes gave the corresponding methyl ketones in good to excellent yields under neutral conditions (additional protic acids and silver salts are not required). A wide range of functional groups, such as allyl ether, benzyl ethers, carboxylic esters, imides, amides, nitro, and halogens, were tolerated. The mild reaction conditions together with the inexpensive feature and easy availability of the catalyst well address the current challenges in the field of alkyne hydration.

A new decarboxylative Csp3–Csp3 coupling approach for the benzylation of ketone enolates has been developed. A variety of raspberry ketone derivatives were conveniently synthesized in good to excellent yields under mild conditions. A crossover reaction shed light on the mechanism of this tandem reaction.

Correction for ‘Decarboxylative Csp3–Csp3 coupling for benzylation of unstable ketone enolates: synthesis of p-(acylethyl)phenols’ by Sasa Wang et al., Chem. Commun., 2016, 52, 9454–9457.