A thiol-free synthesis of alkynyl chalcogenides by the copper-catalyzed C–X (X = S, Se) cross-coupling of alkynyl carboxylic acids with Bunte salts

Carboxylic acids are among the most used feedstock chemicals due to their great structural diversity and easy handling. The use of carboxylic acids and their derivatives in decarboxylative couplings has proven to be a valuable tool for the construction of C−C and C‐heteroatom bonds. This synthetic strategy provides a complementary bond disconnection to traditional cross‐coupling methods. In this review, we provide a comprehensive overview of decarboxylation‐initiated intermolecular C‐heteroatom bond formation, outlining several main mechanistic concepts combined with early examples and highlighting the achievements made in the past decade until January 2021. In these reactions, carboxylic acids and their derivatives undergo initial decarboxylation and then react with other heteroatom electrophiles and nucleophiles, thus replacing the carboxylate group with a valuable and prevalent heteroatom functionality.

Section: Decarboxylative C−chalcogen Bond Formationmentioning

confidence: 99%

Decarboxylation‐Initiated Intermolecular Carbon‐Heteroatom Bond Formation

Zeng¹,

Feceu

Sivendran

et al. 2021

“…[191] The reaction of alkynyl carboxylic acids 318 and diselenides 4 in the presence of CuI/Cs 2 CO 3 /toluene under white light LEDs only gave bis-selenide alkenes 319, whereas tris-selenide alkenes 320 were obtained in the presence of a CuI/Cs 2 CO 3 /NMP (N-methyl-2-pyrrolidone) system. [192][193] The synthesis of mono-selanyl alkene 321 or bisselanyl alkene 322 was successfully achieved in good yields and selectively. When the reactions were carried-out using 5.0 equiv.…”

Section: Synthesis Of Bis-and Tris-selenide Alkenementioning

confidence: 99%

Synthesis of Seleno‐Heterocycles via Electrophilic/Radical Cyclization of Alkyne Containing Heteroatoms

Sonawane

Ninomiya

et al. 2020

containing heterocyclic scaffolds by virtue of their interesting reactivities and a broad range of applications in the medicinal and materials chemistry. This review involves the electrophilic/radical cyclization of alkynes containing heteroatoms which resulted into the novel Se‐heterocycles. The synthesis of seleno‐heterocycles via different nucleophiles including O, N, S, Se, Te, and C‐nucleophiles is exhaustively discussed. Also, one‐pot electrophilic cyclization of 1,3‐diynes and 1,3,5‐triynes was described in details. Furthermore, the various mechanisms underlying the synthesis of selenium‐β‐lactam, carbapenem heterocycle, bis‐ and tris‐selenide alkene, β‐selenosulfonation and selenated alkynes were discussed. The Se‐heterocycles reported in this review allow preparing these selenated compounds bearing the selenium moiety both on the rings (outside) and inside the ring (e. g. selenophenes). The review demonstrates the growing opportunities to construct selenium containing heterocycles from alkynes containing heteroatoms.

“…[2] Therefore, various methodologies were developed to construct novel alkynyl selenides with the formation of new CÀ Se bonds. [3] One representative reaction is the coppercatalyzed decarboxylative CÀ Se cross-coupling, where highly reactive selenating reagents such as phenyl selenocyanate [4] and seleno Bunte salts [5] were used (Scheme 1A). However, issues are accompanied by unstable selenating reagents, expensive catalytic systems and narrow scope of substrates, limiting the development of selenium-containing pharmaceuticals.…”

Section: Introductionmentioning

confidence: 99%

Copper‐Catalyzed Decarboxylative Alkylselenation of Propiolic Acids with Se Powder and Epoxides

Yao

Wang

et al. 2021