1647-16-1Relevant articles and documents
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Blomquist,Taussig
, p. 3505,3507 (1957)
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Ethenolysis reactions catalyzed by imido alkylidene monoaryloxide monopyrrolide (MAP) complexes of molybdenum
Marinescu, Smaranda C.,Schrock, Richard R.,Mueller, Peter,Hoveyda, Amir H.
, p. 10840 - 10841 (2009)
(Chemical Equation Presented) Monoaryloxide-pyrrolide (MAP) olefin metathesis catalysts of molybdenum that contain a chiral bitetralin-based aryloxide ligand are efficient for ethenolysis of methyl oleate, cyclooctene, and cyclopentene. Ethenolysis of 5000 equiv of methyl oleate produced 1-decene (1D) and methyl-9-decenoate (M9D) with a selectivity of >99%, yields up to 95%, and a TON (turnover number) of 4750 in 15 h. Tungstacyclobutane catalysts gave yields approximately half those of molybdenum catalysts, either at room temperature or at 50 °C, although selectivity was still >99%. Ethenolysis of 30000 equiv of cyclooctene to 1,9-decadiene could be carried out with a TON of 22500 at 20 atm (75% yield), while ethenolysis of 10000 equiv of cyclopentene to 1,6-heptadiene could be carried out with a TON of 5800 at 20 atm (58% yield). There is no reason to propose that the efficiency of ethenolysis has been maximized with the most successful catalyst reported here.
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Blomquist,Goldstein
, p. 1001 (1955)
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Nickel-catalyzed deoxygenation of oxiranes: Conversion of epoxides to alkenes
Mori, Takamichi,Takeuchi, Yoshihito,Hojo, Makoto
supporting information, (2020/01/24)
Deoxygenation of epoxides takes place under the catalysis of nickel in the presence of diethylzinc as a deoxygenation agent to yield alkenes. Epoxides with a wide variety of substitution patterns are deoxygenated in this catalytic system to give terminal, 1,1-disubstituted, 1,2-disubstituted, trisubstituted, and tetrasubstituted alkenes in high yields. Reactions of 1,2-disubstituted epoxides we examined proceeded in an E-stereoselective manner. High compatibility with other functional groups through this transformation was also observed.
Unprecedented Selectivity of Ruthenium Iodide Benzylidenes in Olefin Metathesis Reactions
Ivry, Elisa,Lemcoff, N. Gabriel,Nechmad, Noy B.,Phatake, Ravindra,Poater, Albert
, p. 3539 - 3543 (2020/02/04)
The development of selective olefin metathesis catalysts is crucial to achieving new synthetic pathways. Herein, we show that cis-diiodo/sulfur-chelated ruthenium benzylidenes do not react with strained cycloalkenes and internal olefins, but can effectively catalyze metathesis reactions of terminal dienes. Surprisingly, internal olefins may partake in olefin metathesis reactions once the ruthenium methylidene intermediate has been generated. This unexpected behavior allows the facile formation of strained cis-cyclooctene by the RCM reaction of 1,9-undecadiene. Moreover, cis-1,4-polybutadiene may be transformed into small cyclic molecules, including its smallest precursor, 1,5-cyclooctadiene, by the use of this novel sequence. Norbornenes, including the reactive dicyclopentadiene (DCPD), remain unscathed even in the presence of terminal olefin substrates as they are too bulky to approach the diiodo ruthenium methylidene. The experimental results are accompanied by thorough DFT calculations.
Oxidative Dehydroxymethylation of Alcohols to Produce Olefins
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Paragraph 0057; 0058, (2019/09/06)
Catalyst compositions for the conversion of aldehyde compounds and primary alcohol compounds to olefins are disclosed herein. Reactions include oxidative dehydroxymethylation processes and oxidative dehydroformylation methods, which are beneficially conducted in the presence of a sacrificial acceptor of H2 gas, such as N,N-dimethylacrylamide.