S i l i c a -A s s i s t e d R e a c t i o n s o f P y r r o l e s w i t h 1 -A c y l -2 -b r o m a c e t y l e n e s Zinaida V.Abstract: Pyrroles react with 1-acyl-2-bromoacetylenes at room temperature on silica to give 2-acyl-1,1-di(pyrrol-2-yl)ethenes as major products in yields of up to 60%. Under reaction conditions employed, the intermediates (E)-2-(2-acyl-1-bromoethenyl)pyrroles (3-11% isolated yields) either readily exchange the bromine atom for the pyrrole molecule or eliminate HBr to afford 2-(2-acylethynyl)pyrroles, which can be isolated in 9-22% yields by chromatography of the reaction mixture on Al 2 O 3 .Silica plays an important role in organic synthesis and is widely used both in industrial processes and preparative organic reactions. Such reactions often proceed under mild conditions with high chemo-, regio-, and stereoselectivity and allow for simpler product isolation procedures as compared to analogous reactions in solution. 1-3 Synthetic application of solid supports and chromatographic sorbents, including their modified forms, are steadily growing. [4][5][6] The use of silica as a solid support in the C-ethenylation of pyrroles with acylacetylenes proved to be advantageous; it allowed one to achieve significant reaction acceleration, improved regio-and stereoselectivity, and increased yields of adducts. 7,8 Acyl-haloacetylenes have not yet been studied in the reaction with pyrroles, although this would not only contribute to understanding the reactivity of both pyrroles and acylhaloacetylenes, but also provide a route to novel functionalized vinylpyrroles, potent building blocks for design of drugs 9 and advanced materials. 10 Generally, the interaction of haloacetylenes with nucleophiles can proceed via halogen substitution or addition to the triple bond. 11,12 Introduction of strong electron-withdrawing substituents into haloacetylenes not only enhances their reactivity, but also makes the halogen substitution a major pathway of their reactions with nucleophiles. Thus, the first step of interaction of 1-acyl-2-bromoacetylenes with nucleophiles is the exclusive formation of ethynylketones. 13 In the present work, we have for the first time undertaken a study of the reaction of pyrroles 1a-c with 1-acyl-2-bromoacetylenes 2a,b.Under solvent-free conditions, the process is accompanied by strong exothermic effect (sometimes up to explosion) and resinification, whereas in solvents it slows down drastically. For example, in Et 2 O, the reactants 1a and 2b did not show any reaction at room temperature for 24 hours.A successful application of silica as a reaction medium for the C-ethenylation of pyrroles with acylacetylenes 7,8 prompted us to employ this methodology for the addition of pyrroles to 1-acyl-2-bromoacetylenes.According to Scheme 1, pyrroles 1a-c reacted with acylbromoacetylenes 2a,b on silica under mild conditions (room temperature, moderate self-heating, 15 to 30 minutes) to form unexpectedly 2-acyl-1,1-di(pyrrol-2-yl)ethenes 4a-f as major products (in yields of up to 60%, based on...