Yb(OTf) 3 catalyzed mild and regioselective ringopening 1,3-aminothiolation of donor−acceptor (D−A) cyclopropanes using sulfenamides has been demonstrated. The insertion of the C−C σ-bond of D−A cyclopropanes into the S−N σ-bond of sulfenamides allows the synthesis of diverse γ-aminated αthiolated malonic diesters in moderate to good yields (up to 87%) with good functional group compatibility. The stereospecificity of the reaction was demonstrated using enantiomerically pure D−A cyclopropane.

The three-component coupling of tertiary amines, arynes, and aryl selenium bromide or diaryl diselenide as an electrophilic selenium source allowing the synthesis of 2selanyl aniline derivatives is reported. This aminoselenation reaction of arynes installs a C−N and C−Se bond under mild conditions, and the products are formed in moderate to good yields. This reaction is compatible with various functional groups, and the preliminary studies on the mechanism of the reaction is also provided.

The synthetic potential of KI as the iodide source in aryne three-component coupling has been demonstrated using aldehydes as the third component. This mild and transition-metal-free coupling reaction allowed the straightforward synthesis of 2-iodobenzyl alcohols in moderate to good yields with good functional group compatibility. Moreover, KBr and KCl could be used as the nucleophilic trigger in this aryne multicomponent coupling (MCC) and N-methylisatin and CO2 could be used as the electrophilic third components.

The synthetic utility of NaN3 as the azide component in the [3 + 2] annulation with arynes generated from 2-(trimethylsilyl)­aryltriflates resulting in the transition-metal-free synthesis of N-H and N-aryl benzotriazoles has been demonstrated. Using CsF as the fluoride source in CH3CN, the N-H benzotriazoles are formed in high selectivity instead of the expected azidobenzene. Interestingly, N-aryl benzotriazoles are formed using KF and THF as solvent in an open-flask reaction. Moreover, a method for the N1-arylation of benzotriazole is also presented.

The synthetic potential of thiophenols as a protic nucleophilic trigger in the transition-metal-free and Grignardreagent-free three-component coupling involving arynes is demonstrated. Employing aldehydes as the third component, the reaction allowed the mild and broad scope synthesis of 2-arylthio benzyl alcohol derivatives in good yields. Moreover, selenophenol could be used as the nucleophilic trigger, and activated ketones could be used as the third component in this reaction.

A transition-metal-free, three-component, and diastereoselective [6 + 3] annulation reaction employing tropone, imino esters, and arynes allowing the synthesis of bridged azabicyclo[4.3.1]­decadienes is demonstrated. The key nitrogen ylides for the [6 + 3] annulation were generated by the addition of imino esters to the arynes followed by a proton transfer. The nitrogen ylides undergo a regioselective addition to tropone to furnish the desired products in moderate to good yields with good functional group tolerance under mild conditions.

The direct C2‐functionalization of pyridines through a transition‐metal‐free protocol by using aryne multicomponent coupling is demonstrated. The reaction allowed a broad‐scope synthesis of C2‐substituted pyridine derivatives bearing the −CF3 group in good yields with α,α,α‐trifluoroacetophenones as the third component. Activated keto esters could also be employed as the third component in this formal 1,2‐di(hetero)arylation of ketones. Performing the reaction under dilute conditions inhibited the competing pyridine–aryne polymerization pathway. Nucleophilic attack by the initially generated pyridylidene intermediate on the carbonyl followed by an SNAr process resembling the Smiles rearrangement affords the desired products.

Traditional radical-mediated ring-opening of bicyclo[1.1.0]butanes (BCBs) for cyclobutane synthesis suffers from poor diastereoselectivity. Although few reports on BCB ring-opening via polar mechanisms are available, the Lewis acid-catalyzed diastereoselective ring-opening of...