1415237-87-4Relevant articles and documents
Synthesis of Substituted β-Styrylmalonates by Sequential Isomerization of 2-Arylcyclopropane-1,1-dicarboxylates and (2-Arylethylidene)malonates
Borisov, Denis D.,Chermashentsev, Grigorii R.,Novikov, Roman A.,Tomilov, Yury V.
, p. 2253 - 2259 (2021)
A method has been developed for the synthesis of substituted β-styrylmalonates by conversion of 2-arylcyclopropane-1,1-dicarboxylates (ACDCs) in the presence of gallium trichloride into the corresponding- 1,2-zwitterionic intermediates or (2-arylethyl-idene)malonates, followed by treatment with pyridine at room temperature leading to an isomerization of the emerging double bond. This method allows one to expand these reactions to include ACDCs with acceptor substituents at the aromatic ring.
Ionic Ga-Complexes of Alkylidene- And Arylmethylidenemalonates and Their Reactions with Acetylenes: An In-Depth Look into the Mechanism of the Occurring Gallium Chemistry
Novikov, Roman A.,Denisov, Dmitry A.,Potapov, Konstantin V.,Tkachev, Yaroslav V.,Shulishov, Evgeny V.,Tomilov, Yury V.
, p. 14381 - 14390 (2018)
A new synthetic concept was suggested in the chemistry of substituted methylidenemalonates that enables their utilization as 1,2-zwitterionic synthons. This strategy is to generate liquid ionic Ga complexes from methylidenemalonates and GaHal3with a strict 3/4 composition and then use them in further synthesis. A number of complexes with different metal halides have been synthesized and studied in detail. The unique properties of gallium among all metals have been demonstrated and explained. On the basis of the discovered new class of gallium complexes of methylidenemalonates, a number of novel reactions with acetylenes have been elaborated, which are unknown in the conventional chemistry of methylidenemalonates. The main demonstrated process is a three-component addition to a triple bond involving halide anions, leading to the formation of polyfunctional vinyl halides with highE-selectivity. The mechanism has been studied experimentally in fine detail. Application of specially optimized71Ga NMR spectroscopy makes it possible to take an in-depth look into the gallium chemistry in a new light. In particular, the key participation of GaHal4-anions in the occurring transformations has been established.
Four-Membered Cycle Formation Challenge: GaCl3-Promoted Formal [2+2]-Cycloaddition of Donor–Acceptor Cyclopropanes to Bicyclobutylidene
Zotova, Maria A.,Novikov, Roman A.,Volodin, Alexander D.,Korlyukov, Alexander A.,Tkachev, Yaroslav V.,Korolev, Victor A.,Tomilov, Yury V.
, p. 4207 - 4214 (2019)
The first selective process of formal [2+2]-cycloaddition of donor–acceptor cyclopropanes (DAC) to multiple C–C bonds to form a four-membered ring in the product has been developed. Bicyclobutylidene is used do demonstrate this reaction. The process is promoted by GaCl3 and occurs through generation of 1,2-zwitterionic intermediates. A carbocationic rearrangement occurs in the bicyclobutylidene moiety. It results in expansion of both cyclobutane rings into five-membered ones and formation of a [2.3.3]propellane skeleton in the final product.
