Domino reactions of thiopyrano[4, 3-b]indole-3(5H)-thiones and dimethyl acetylenedicarboxylate: Quantum chemical investigation and experiment. (4th March 2023)

• Record Type: Journal Article
• Authors: Suzdalev, Konstantin F.; Gazizova, Julia V.; Tkachev, Valery V.; Kletskii, Mikhail E.; Lisovin, Anton V.; Burov, Oleg N.; Steglenko, Dmitriy V.; Kurbatov, Sergey V.; Shilov, Gennadii V.
• Is Part Of: Journal of sulfur chemistry. Volume 44:Number 2(2023)
• Page Start: 248
• Page End: 259
• Publication Date: 2023-03-04
• Subjects: Domino-reaction -- rearrangement -- DMAD -- 2H-thiopyran-2-thione -- cycloaddition; Sulfur -- Periodicals; Chemistry, Inorganic -- Periodicals; 546.72305
• DOI: 10.1080/17415993.2022.2139147
• Languages: English
• ISSNs: 1741-5993

Abstract

Abstract : Reaction of thiopyrano[4, 3- b ]indole-3(5 H )-thiones and dimethyl acetylenedicarboxylate (DMAD) proceeds via two competing cascade pathways. Initially, both the pathways begin from thiocarbonyl sulfur and acetylene carbon atoms interaction. Then two parallel processes take place: an alkyne–thiocarbonyl metathesis and a (3 + 2) cycloaddition. In the next stages, in both cases, thiophene ring formation and thiopyran ring opening proceed. Finally, (4 + 2) cycloaddition reactions of intermediate thioketones and a second equivalent of DMAD leads to the resulting thiopyrano[4, 3- b ]indole derivatives bearing thienyl substituent. The kinetic and thermodynamic characteristics of both pathways were compared on the basis of DFT and ab initio 6-311++G(d, p) quantum chemical calculations. GRAPHICAL ABSTRACT: UF0001