Three types of sulfides bearing a propargyl or an alkynyl moiety have been studied in cyclocarbopalladation/cross-coupling domino palladium-catalyzed sequences. The reactivity of different types of sulfured starting materials has been compared as well as the difference in behavior of these compounds depending on the type of cross coupling ending the domino sequence. It appeared that these cascades were constantly more efficient on the propargyl benzyl thioether. In addition, it has been demonstrated that domino sequences ending with Stille, Suzuki–Miyaura, or Mizoroki–Heck lead efficiently and selectively to the desired cyclized products. Notably, when the introduction of an alkyne is targeted at the end of the cascade, it appeared that the Sonogashira coupling leads every time to the desired cyclic product in the mixture with the product resulting from the direct coupling between the aryl moiety of the substrate and the alkyne used as partner. Finishing the domino sequence with a Stille coupling instead of a Sonogashira one allowed improving significantly the ratio of the mixture in favor of the desired cyclized compound.Divers substrats de type thioéther portant une partie propargylique ou acétylénique ont été étudiés dans des séquences domino pallado-catalysées de type cyclocarbopalladation/couplage croisé. La comparaison des différents types de composés soufrés en termes de réactivité a été réalisée ainsi que celle des comportements de ces mêmes substrats en fonction du type de couplage croisé terminant la séquence domino. Il est apparu que ces cascades réactionnelles sont systématiquement plus efficaces sur un précurseur de type benzyle propargyle thioether. De plus, il a été constaté que les réactions domino se terminant par un couplage de Stille, de Suzuki–Miyaura ou de Mizoroki–Heck conduisaient toutes, de manière efficace et sélective, au composé cyclique soufré. De manière notable, lorsque l'objectif était d'introduire un alcyne en fin de séquence réactionnelle, il est apparu que le couplage de Sonogashira conduisait systématiquement à un mélange du produit cyclisé désiré avec le produit issu du couplage direct entre l'alcyne utilisé et la partie aromatique du substrat. En finissant la séquence domino avec un couplage de Stille, il a été possible d'améliorer de manière significative le ratio du mélange en faveur du produit cyclique désiré.

Organic thiocyanates are important synthetic intermediates to access valuable sulfur-containing compounds. In this review the different methods for their preparation and their synthetic applications will be presented. The literature of the last 15 years will be covered, highlighting selected recent advances in the chemistry of this class of compounds. We hope to offer chemists the tools to have a good grasp of this singular functionality and open the door to further progress in this chemistry.

An unprecedented three-component reaction involving a 2,2′-diaminodiaryl disulfide, copper cyanide, and an electrophile is described. This transformation is based on an oxidative copper-mediated S-cyanation as a key step and involves a cyanation/cyclization/acylation domino sequence enabling a rapid and efficient synthesis of diversely substituted 2-aminobenzothiazole derivatives. Notably, this reaction proceeds via an original mechanism involving an intermolecular migration of the acyl group.

Cyclocarbopalladation/cross-coupling cascade reactions were applied for the first time in a sulfur series and represent an efficient route to access sulfur heterocycles. Stille or Suzuki–Miyaura cross-coupling was successfully used as the final reaction. The products are original benzothiolane and isothiochromane scaffolds with a stereodefined tetrasubstituted exocyclic double bond. To illustrate the application of this method to the synthesis of bioactive molecules, a sulfur analogue of the anticancer agent tamoxifen was prepared as a potential selective estrogen-receptor modulator.

A new asymmetric three-component domino process, based on a diastereoselective hetero-Diels–Alder reaction, involving an aldehyde, an alkene, and a chiral thiocarbamate was developed. The chiral auxiliary is directly removed during this process, leading to enantioenriched 2H-1,3-thiazin-2-ones with up to 96% ee.

Organic thiocyanates are important synthetic intermediates to access valuable sulfur-containing compounds. In this review the different methods for their preparation and their synthetic applications will be presented. The literature of the last 15 years will be covered, highlighting selected recent advances in the chemistry of this class of compounds. We hope to offer chemists the tools to have a good grasp of this singular functionality and open the door to further progress in this chemistry.