Mechanism of С-Н cyclization of alkynylanthraquinones into thienoanthraquinones with the participation of sodium sulfide

• Published in: Tetrahedron 2017-11, Vol.73 (44), p.6334-6340
• Main Authors: Fedenok, Lidiya, Dultsev, Fedor, Barabanov, Igor, Polyakov, Nikolay
• Format: Article
• Language: English
• Subjects: Alkynyl-9,10-anthraquinones; Heterocyclization; Mechanism; Sodium sulfide; Thienoanthraquinones
• ISSN: 0040-4020; 1464-5416
• DOI: 10.1016/j.tet.2017.09.023

The CH-cyclization of alkynyl-9,10-anthraquinones 1 into thienoanthraquinones 2 is shown to be initiated by the neutral S2 molecule and not by the sulfide anion as it is assumed in the existing model of CH-cyclization with the nucleophiolic substitution of H. The formation of S2 takes place in the reaction medium due to the partial reduction of the substrate 1 by Na2S into the corresponding anthrahydroquinone, which is inactive in the main reaction. We present a new cyclization mechanism with the key stage involving the electrophilic displacement of H, which results in the formation of the reaction product 2 and elimination of S. In the reaction medium atomic sulfur is transformed into S2, which initiates the next cyclization act. This determines the chain nature of cyclization with the participation of S2. Within this model, the route to increase the yield of target thienoanthraquinones is proposed through the introduction of a neutral quinone able to generate S2 by means of easy reduction. [Display omitted]