Acetylene as a Driving and Organizing Molecule in One‐Pot Transition‐Metal‐Free Synthesis of Furans using Chalcones and their Analogues

Abstract

Acetylene reacts with chalcones and their heterocyclic analogues in NaO t Bu/DMSO catalytic system (70 8C, 15 min) to afford substituted furans in ay ield of up to 85 %, thus providing as imple and technologically feasible access to rare furan compounds.Acetylenea nd furans and their derivativesa re among the fundamental molecules in organic chemistry.I nt he last decade, acetylene and its derivatives hasr apidly regainedt he position of important building blocks for the rational pot, atom and step economy (PASE) [1] construction of complex moleculeso f ad esirable structure that is evidenced by al arge number of publications (experimental, reviews, [2] and monographs [3] ). The role of acetylene in chemistry has been even more reinforced by its recognition as renewable feedstock [4] due to the development of its production from charcoal [5] throughc alcium carbide.The furan structures are common for many bioactive natural products [6] and important pharmaceuticals, [7] including antitumor ones. [8] Furansa re also widely used as synthetic intermediates to design structurally diversem olecules [9] and numerous functional groups. [10] Despite the existing plethora of methods for the constructiono ft he furan ring, [11] importance of these compounds demands for continuous search and development of more simple and modulars yntheses in terms of PASE approach, [1] especially those allowing diversification of their structure.Recently,w eh ave disclosed one-pott ransition-metal-free assembly of furans from ketones and two molecules of acetylene in KOH/DMSOc atalytic system. [12] The key intermediates of this cascade reaction were postulated to be a,b-ethylenic ketones generated by the previously discovered base-catalyzed addition of ketones to acetylenes. [13] Here we report that verifica-Supportinginformation for this article can be found under: https://doi.

Acetylenes in the Superbase-Promoted Assembly of Carbocycles and Heterocycles

“…This finding inspired us to develop a one-pot synthesis of uniquely variously substituted furans 27 from acetylene and chalcones (Scheme 18). 32 The reaction starts with nucleophilic addition of an acetylenic carbanion to the electrophilic double bond of the chalcone. This assembly also tolerates arylacetylenes (Scheme 19), including ones having electron-donating or -accepting substituents.…”

“…This assembly also tolerates arylacetylenes (Scheme ), including ones having electron-donating or -accepting substituents. However, the yields are somewhat lower …”

Densely Packed Chemical Synthesis Equipment by 3D Spatial Design and Additive Manufacturing: Acetylene Generation Cartridge

“…In most studies, acetylene transformations are carried out in autoclaves under high pressure. In the case of catalytic reactions, this probably indicates low activity of catalysts. , Previously, our group showed that 1,2-bis­(arylthio)­ethenes can be synthesized using an atom-economical approach by the nickel-catalyzed addition of diaryl disulfide to acetylene in solution at a pressure close to atmospheric …”

Recent Developments in the Synthesis of Organoselenium Compounds Based on the Reactions of Organic Diselenides with Acetylenes

“…The Favorsky reaction of acetylenes with carbonyl compounds underlies a number of the methods used in industry for the production of valuable reagents and materials [47]. Developing Favorsky's scientific heritage in the A. E. Favorsky Irkutsk Institute of Chemistry, important fundamental contributions to the chemistry of acetylene and its derivatives were made by Trofimov and co-workers [49][50][51][52][53][54][55][56].…”