Metal Catalysis in Thiolation and Selenation Reactions of Alkynes Leading to Chalcogen-Substituted Alkenes and Dienes

Abstract

This review covers recent achievements in metal‐catalyzed Z−H and Z−Z (Z=S, Se) bond addition to the triple bonds of alkynes—a convenient and atom‐efficient way to carbon‐element bond formation. Various catalytic systems (both homogeneous and heterogeneous) developed to date to obtain mono‐ and bis‐chalcogen‐substituted alkenes or dienes, as well as carbonyl compounds or heterocycles, starting from simple and available alkynes and chalcogenols or dichalcogenides are described. The right choice of metal and ligands allows us to perform these transformations with high selectivities under mild reaction conditions, thus tolerating unprotected functional groups in substrates and broadening ways of further modification of the products. The main aim of the review is to show the potential of the catalytic methods developed in synthetic organic chemistry. Thus, emphasis is made on the scope of reactions, types of products that can be selectively formed, convenience, and scalability of the catalytic procedures. A brief mechanistic description is also given to introduce new readers to the topic.

Selectivity control in thiol–yne click reactions via visible light induced associative electron upconversion

“…[1][2][3][4][5] Many homogeneous and heterogeneous catalytic systems were developed for the addition reaction of thiols to alkynes, but there is still demand for a selective and simple catalytic synthesis of Markovnikov and anti-Markovnikov vinyl suldes. [6][7][8] Reported methods for selective thiol-yne reactions require expensive metal complexes or special ligands and harsh conditions. Moreover, most catalytic systems are limited in scope and metal catalyzed reactions may contaminate the products with metal traces.…”

(Z,Z)-Selanediylbis(2-propenamides): Novel Class of Organoselenium Compounds with High Glutathione Peroxidase-Like Activity. Regio- and Stereoselective Reaction of Sodium Selenide with 3-Trimethylsilyl-2-propynamides

“…The main methods for the preparation of vinyl selenides include a transition metal catalyzed coupling of vinyl halides with diselenides or selenols [ 13 , 14 , 15 , 16 ], reactions of thiols or chalcogenolates with selenoalkynes [ 14 , 17 , 18 ], and addition of selenium-centered nucleophiles to acetylenes [ 8 , 14 , 19 , 20 , 21 , 22 , 23 ].…”

“…One of the most useful and atom-economic methods is based on addition reactions of selenoles or selenolate anions with acetylenes [ 8 , 14 , 19 , 20 , 21 , 22 ]. Examples of these reactions refer mainly to vinyl selenides containing aliphatic or aromatic substituents at the β-carbon atom of the double bond.…”

Copper-Catalyzed Three Component Regio- and Stereospecific Selenosulfonation of Alkynes: Synthesis of (E)-β-Selenovinyl Sulfones

“…For example, alkynes sulfonative difunctionalization, such as halosulfonylation, sulfonyloxidation, sulfonamination, and sulfonylcarbonation, has been successfully realized for the synthesis of various sulfonative difunctionalization products. Vinyl selenides are useful synthetic intermediates and therapeutic entities that display a wide spectrum of biological activities, thus rendering these motifs highly important synthetic targets . β-Selenovinyl sulfones could be obtained through radical selenosulfonation of alkynes and Se-phenyl p -tolueneselenosulfonate (Scheme a), which usually need to be prepared through the reaction of sulfinates, sulfonohydrazides, or selenenyl halides with benzeneseleninic acid, or sodium sulfonates with diphenyl diselenide .…”