15185-11-2Relevant articles and documents
Whitesides et al.
, p. 6542 (1969)
ESR Study of γ-Irradiated Substituted Norbornanes in Thiourea Clathrate and Adamantane Matrix. Novel 2-Norbornyl-Type Radicals
Faucitano, A.,Buttafava, A.,Martinotti, F. Faucitano,Cesca, S.
, p. 367 - 374 (1981)
The γ irradiation at 77 K of 2-methyl-2-ethylbicycloheptane and of 2-methylene-2-ethylidenebicycloheptene in the state of thiourea adducts leads to formation of 2-methyl- and 2-ethylnorbornyl radicals by loss of hydrogen atoms at the substituent sites or by partial hydrogenation of the double bonds.On warming above 77 K after irradiation, the 2-alkylnorbornyls add to double bonds of neighboring molecules yielding new adduct radicals alkylnorbornyl.The reactions can be reversed by UV irradiation at 77 K, thus suggesting that the addition does not proceed beyond the first step.A reaction model based on the geometrical control by the molecular packing within the clathrate channels has been proposed.The irradiation of 2-ethylidenenorbornene in the state of thiourea clathrate or trapped in adamantane matrix yields an allyl-type radical by loss of a hydrogen atom from the methyl group.The structure and ESR properties of 2-alkylnorbornyls and of the allylnorbornyl have been investigated by MO methods to the INDO and extended Hueckel levels of approximation.
Environmentally responsible, safe, and chemoselective catalytic hydrogenation of olefins: ppm level Pd catalysis in recyclable water at room temperature
Gallou, Fabrice,Gao, Eugene S.,Lipshutz, Bruce H.,Takale, Balaram S.,Thakore, Ruchita R.
supporting information, p. 6055 - 6061 (2020/10/14)
Textbook catalytic hydrogenations are typically presented as reactions done in organic solvents and oftentimes under varying pressures of hydrogen using specialized equipment. Catalysts new and old are all used under similar conditions that no longer reflect the times. By definition, such reactions are both environmentally irresponsible and dangerous, especially at industrial scales. We now report on a general method for chemoselective and safe hydrogenation of olefins in water using ppm loadings of palladium from commercially available, inexpensive, and recyclable Pd/C, together with hydrogen gas utilized at 1 atmosphere. A variety of alkenes is amenable to reduction, including terminal, highly substituted internal, and variously conjugated arrays. In most cases, only 500 ppm of heterogeneous Pd/C is sufficient, enabled by micellar catalysis used in recyclable water at room temperature. Comparison with several newly introduced catalysts featuring base metals illustrates the superiority of chemistry in water.
