Arynes are among the most active organic intermediates and have found numerous applications in expeditious preparation of substituted arenes. In the past 20 years, chemists have witnessed a resurgence in aryne chemistry, which is mainly attributed by the extensive utilization of Kobayashi's method, a fluoride-induced removal of the TMS group with concomitant departure of its ortho OTf group on o-silylaryl triflates. Nowadays, o-silylaryl triflates are the most frequently employed aryne precursors. This review provides an overview of the history of Kobayashi's method, its methodological achievements, and its applications in the synthesis of natural products, bioactive molecules, and polycyclic aromatic hydrocarbons.

o-Silylaryl Triflates: A Journey of Kobayashi Aryne Precursors.

A leap forward in sulfonium salt and sulfur ylide chemistry

The direct methylation of N-heterocycles is an important transformation for the advancement of pharmaceuticals, agrochemicals, functional materials, and other chemical entities. Herein, the unprecedented C(sp2 )-H methylation of iminoamido heterocycles as nucleoside base analogues is described. Notably, trimethylsulfoxonium salt was employed as a methylating agent under aqueous conditions. A wide substrate scope and excellent level of functional-group tolerance were attained. Moreover, this method can be readily applied to the site-selective methylation of azauracil nucleosides. The feasibility of gram-scale reactions and various transformations of the products highlight the synthetic potential of the developed method. Combined deuterium-labeling experiments aided the elucidation of a plausible reaction mechanism.

C-H Methylation of Iminoamido Heterocycles with Sulfur Ylides*

Synthesis of Bicyclo[4.1.0]tetrahydropyridazines by a Sequential [4 + 2] and [1 + 2] Annulation Reaction of Azoalkenes and Crotonate-Derived Sulfur Ylides.

Benzothiophene, benzofuran, indole, and indene derivatives are privileged heterocyclic motifs. These are present in a wide range of bioactive natural products and pharmaceutical drugs and are the subject of materials science research. However, the construction of benzothiophene, benzofuran, indole, and indene frameworks have been long-standing challenges to organic chemists. In this review, we classify the derivatives of four structures synthesized from 2-benzylidene-1-benzofuran-3-one and their analogues in terms of their ring size (from three- to ten-membered) and type (fused or spiro), as well as summarizing the developments of this field. Finally, we discuss the ring opening and 1,4-addition reactions.

Recent Advances in the Cycloaddition Reactions of 2‐Benzylidene‐1‐benzofuran‐3‐ones, and Their Sulfur, Nitrogen and Methylene Analogues

Substrate-controlled domino reactions between thioaurones or their analogues and crotonate-derived sulfur ylides were developed and produced a broad spectrum of benzothiophene-fused pyran derivatives, substituted chromene derivatives. In these reactions, crotonate-derived sulfur ylides acting as two-carbon synthons (α and β carbons or β and γ carbons) in annulation reactions are reported for the first time. These investigations nicely complement and expand previously studied reactions of crotonate-derived sulfur ylides. In addition, reaction mechanisms for these domino reactions are proposed, one of which is supported by DFT calculations.

Substrate-Controlled Domino Reactions of Crotonate-Derived Sulfur Ylides: Synthesis of Benzothiophene Derivatives.

Construction of Eight-Membered Cyclic Diaryl Sulfides via Domino Reaction of Arynes with Thioaurone Analogues and DFT Study on the Reaction Mechanism.

Lysophosphatidylcholine acyltransferase 1 promotes epithelial-mesenchymal transition of hepatocellular carcinoma via the Wnt/β-catenin signaling pathway.

Wenhuan Ding

Papers

Substrate-Controlled Domino Reactions of Crotonate-Derived Sulfur Ylides: Synthesis of Benzothiophene Derivatives.

Construction of Eight-Membered Cyclic Diaryl Sulfides via Domino Reaction of Arynes with Thioaurone Analogues and DFT Study on the Reaction Mechanism.

Lysophosphatidylcholine acyltransferase 1 promotes epithelial-mesenchymal transition of hepatocellular carcinoma via the Wnt/β-catenin signaling pathway.

Construction of Polyaromatic Hydrocarbons Containing Sulfur and Nitrogen via Controllable Domino Reactions and DFT Studies.