62781-99-1Relevant articles and documents
Group-Transfer Reactions of a Cationic Iridium Alkoxycarbene Generated by Ether Dehydrogenation
Chapp, Scott M.,Schley, Nathan D.
, p. 7143 - 7149 (2020)
Despite broad interest in metal carbene complexes, there remain few examples of catalytic transformations of ethers that proceed via alkoxycarbene intermediates generated by α,α-dehydrogenation. We demonstrate that both neutral and cationic alkoxycarbene derivatives are accessible via ether dehydrogenation at a PNP(iPr)4 pincer-supported iridium complex (PNP(iPr)4 = 2,6-bis((diisopropylphosphino)methyl)pyridine). Both cationic and neutral alkoxycarbene complexes undergo group transfer imination with azides, with the cationic derivative serving as a more efficient catalyst for cyclopentyl ether imination. Mechanistic studies support an iridium(I)dinitrogen complex as the resting state in the dark and a role for light-promoted N2 dissociation. Isoamyl nitrite and phenyl ethyl ketene are also found to engage with the cationic alkoxycarbene complex in formal alkoxide and O atom transfer reactions, respectively. In the former case an isolable dialkoxyalkyliridium complex is obtained, representing only the second example of a structurally characterized dialkoxyalkyl complex of a transition metal.
Rhodes,Y.E.,Takino,T.
, p. 4469 - 4470 (1968)
Consecutive addition esterification and hydrolysis of cyclic olefins catalyzed by multi-SO3H functionalized multi heteropolyanion-based ionic hybrids undersolvent-free conditions
Zheng, Guocai,Li, Xinzhong
, p. 933 - 941 (2019/03/17)
An efficient protocol for the synthesis of cycloalkyl carboxylates and alcohols from cyclic olefins is described. The cyclic olefins were converted to corresponding target molecules under solvent-free conditions catalyzed by two novel multi-SO3H functionalized multi heteropolyanion-based ionic hybrids through one-pot consecutive addition esterification and hydrolysis reactions. This approach has several advantages, including high yield, simple workup and simple purification.
Method of using swelling-able acidic poly(ionic liquid) to catalyze esterification between formic acid and alkenes to prepare formate
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Paragraph 0029; 0030; 0031; 0033; 0034; 0042; 0043-0046, (2018/11/04)
The invention discloses a method of using swelling-able acidic poly(ionic liquid) to catalyze esterification between formic acid and alkenes to prepare formate. According to the method, an acidic poly(ionic liquid) that can swell in formic acid is synthesized at first; 1-vinyl-3-alkyl imidazolium bromine salt ionic liquid and sodium acrylate are taken as the copolymerization monomers, and throughfree radical polymerization and acidification that uses an acid with an equal molar weight, the poly(ionic liquid) is prepared. The poly(ionic liquid) is taken as a catalyst to catalyze the esterification reactions between formic acid and alkenes; the catalytic activity of the poly(ionic liquid) is equal to that of a homogeneous catalyst and the selectivity is higher than that of a homogeneous catalyst or a heterogeneous catalyst. The swelling-able acidic poly(ionic liquid) is used to catalyze the esterification reactions between formic acid and alkenes, the characteristic that the poly(ionicliquid) can swell in formic acid is utilized, the poly(ionic liquid) is fully dispersed in the substrate, at the same time, the active centers of the acid are immobilized on the poly(ionic liquid), thus the active centers can fully contact with the substrate, and the catalytic efficiency is largely improved.
