28267-32-5Relevant academic research and scientific papers
The scope and mechanism of palladium-catalysed Markovnikov alkoxycarbonylation of alkenes
Li, Haoquan,Dong, Kaiwu,Jiao, Haijun,Neumann, Helfried,Jackstell, Ralf,Beller, Matthias
, p. 1159 - 1166 (2016/11/28)
Hydroesterification reactions represent a fundamental type of carbonylation reaction and constitute one of the most important industrial applications of homogeneous catalysis. Over the past 70 years, numerous catalyst systems have been developed that allow for highly linear-selective (anti-Markovnikov) reactions and are used in industry to produce linear carboxylates starting from olefins. In contrast, a general catalyst system for Markovnikov-selective alkoxycarbonylation of aliphatic olefins remains unknown. In this paper, we show that a specific palladium catalyst system consisting of PdX2/N-phenylpyrrole phosphine (X, halide) catalyses the alkoxycarbonylation of various alkenes to give the branched esters in high selectivity (branched selectivity up to 91%). The observed (and unexpected) selectivity has been rationalized by density functional theory computation that includes a dispersion correction.
Transformations of peroxide products of oleic acid ozonolysis at treatment with hydroxylamine and semicarbazide hydrochlorides
Ishmuratov, G. Yu.,Yakovleva,Botsman,Legostaeva, Yu. V.,Nazarov,Baidimirov
, p. 610 - 614 (2015/07/02)
Peroxide products of oleic acid ozonolysis treated with semicarbazide and hydroxylamine hydrochlorides in methanol are predominantly converted into methyl nonanoate and dimethyl nonanedioate, in 2-propanol, into isopropyl nonanoate and monoisopropyl ester of nonanedioic acid, and also into nonanenitrile, in tetrahydrofuran and in a mixture of acetic acid with dichloromethane, into nonanoic and nonanedioc acids, and also in nonanal oxime and 9-(hydroxyimino)nonanoic acid.
Regioselective Pd-Catalyzed Methoxycarbonylation of Alkenes Using both Paraformaldehyde and Methanol as CO Surrogates
Liu, Qiang,Yuan, Kedong,Arockiam, Percia-Beatrice,Franke, Robert,Doucet, Henri,Jackstell, Ralf,Beller, Matthias
supporting information, p. 4493 - 4497 (2015/04/14)
In recent years, considerable effort has focused on the development of novel carbonylative transformations using CO surrogates. Consequently, toxic CO gas can be replaced by more convenient inorganic or organic carbonyl compounds. Herein, the first regioselective methoxycarbonylation of alkenes with paraformaldehyde and methanol as CO substitutes is reported. This new procedure is applicable to a series of alkenes in the presence of a palladium catalyst under relatively mild conditions and is highly atom efficient.
Fragmentation of chloroperoxides: Hypochlorite-mediated dehydration of hydroperoxyacetals to esters
Fisher, Thomas J.,Dussault, Patrick H.
experimental part, p. 5615 - 5617 (2010/10/21)
Hypochlorites efficiently dehydrate hydroperoxyacetals to furnish the corresponding esters. The reaction, which can be accomplished with stoichometric Ca(OCl)2 or with catalytic amounts of t-BuOCl, appears to involve formation and heterolytic fragmentation of secondary chloroperoxides, species not previously described in solution chemistry.
