Modular Synthesis of Tetrasubstituted Vinyl Sulfides via One-Pot Sequential Carbene Transfer Reaction from Thiols with α-Diazo Carbonyl Compounds.

We present a one-pot reaction that offers an efficient approach to synthesizing tetrasubstituted vinyl sulfides with high stereoselectivity. This method involves the sequential Wolff rearrangement, ylide formation, and [1,4]-aryl transfer by utilizing aryl and alkyl thiols and α-diazo carbonyl compounds as substrates. Notably, this reaction features commercially available materials, straightforward operation, atom economy, and broad substrate scope. Moreover, the primary photophysical properties (aggregation-induced emission effect) of the products were also investigated, which might be useful in functional materials via structural modification.

Enantioselective para-C(sp2 )-H Functionalization of Alkyl Benzene Derivatives via Cooperative Catalysis of Gold/Chiral Brønsted Acid.

An asymmetric para-C(sp2 )-H bond functionalization of alkyl benzene derivatives was successfully developed via cooperative catalysis of gold and chiral phosphoric acid (CPA), leading to synthetically useful chiral 1,1-diaryl motifs. Chiral phosphoric acid, ligand, and molecular sieves were found to be crucial for enantioselectivity control of this transformation. The salient features of this protocol include mild conditions, high efficiency, commercially available starting materials, highly chemo- and site- as well as enantioselective aromatic C-H functionalization, broad substrate scope, and extensive applications of the chiral products. The mechanistic studies suggested that two CPAs might be involved in chiral induction.

Dearomative Iodocyclization of N-(o-Alkynyl)aryl Isoindole.

We present a dearomative iodocyclization of N-(o-alkynyl)aryl isoindole here, which affords various biologically active benzoindoleazine skeletons containing alkenyl iodine. The products can further undergo cycloaddition or coupling reactions to afford a series of highly functionalized N-fused polycyclic scaffolds.

Highly Stereoselective Synthesis of Tetrasubstituted Vinyl Selenides via Rhodium-Catalyzed [1,4]-Acyl Migration of Selenoesters and Diazo Compounds.

Herein, we disclose a highly stereoselective Rh(II)-catalyzed 1,4-acyl rearrangement of selenium esters and α-diazo carbonyl compounds, which provides an efficient method for synthesizing tetrasubstituted vinyl selenides. Furthermore, this reaction also offers a synthetic tool for medium and large ring compounds.

Modular and stereoselective synthesis of tetrasubstituted vinyl sulfides leading to a library of AIEgens.

Tetraarylethylenes exhibit intriguing photophysical properties and sulfur atom frequently play a vital role in organic photoelectric materials and biologically active compounds. Tetrasubstituted vinyl sulfides, which include both sulfur atom and tetrasubstituted alkenes motifs, might be a suitable skeleton for the discovery of the new material molecules and drug with unique functions and properties. However, how to modular synthesis these kinds of compounds is still challenging. Herein, a chemo- and stereo-selective Rh(II)-catalyzed [1,4]-acyl rearrangements of α-diazo carbonyl compounds and thioesters has been developed, providing a modular strategy to a library of 63 tetrasubstituted vinyl sulfides. In this transformation, the yield is up to 95% and the turnover number is up to 3650. The mechanism of this reaction is investigated by combining experiments and density functional theory calculation. Moreover, the "aggregation-induced emission" effect of tetrasubstituted vinyl sulfides were also investigated, which might useful in functional material, biological imaging and chemicalnsing via structural modification.