- Acid-Promoted Hydroformylative Synthesis of Alcohol with Carbon Dioxide by Heterobimetallic Ruthenium-Cobalt Catalytic System
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The acid-aided heterobimetallic ruthenium-cobalt catalytic system for the reductive hydroformylation with carbon dioxide was established. Various alkenes, including waste from biomass and petroleum industry, could be upgraded to valuable alcohols with this protocol. Acid-promoted reverse water-gas shift (RWGS), thereby accelerating the hydroformylative synthesis of alcohol. The theoretical computations revealed that acid promoted RWGS by facilitating the dehydroxylation of ruthenium hydroxy carbonyl intermediate.
- Zhang, Xuehua,Tian, Xinxin,Shen, Chaoren,Xia, Chungu,He, Lin
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p. 1986 - 1992
(2019/03/17)
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- Ruthenium-catalyzed hydroformylation/reduction of olefins to alcohols: Extending the scope to internal alkenes
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In the presence of 2-phosphino-substituted imidazole ligands and Ru 3(CO)12 or Ru(methylallyl)2(COD) direct hydroformylation and hydrogenation of alkenes to alcohols takes place. In addition to terminal alkenes, also more challenging internal olefins are converted preferentially to industrially important linear alcohols in high yield (up to 88%) and regioselectivity (n:iso up to 99:1).
- Wu, Lipeng,Fleischer, Ivana,Jackstell, Ralf,Profir, Irina,Franke, Robert,Beller, Matthias
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supporting information
p. 14306 - 14312
(2013/10/21)
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- Transition-metal-catalyzed cyclopropanation of nonactivated alkenes in dibromomethane with triisobutylaluminum
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The cyclopropanation of nonactivated alkenes with inexpensive triisobutylaluminum (TIBA), in dibromomethane as solvent and reagent, is efficiently catalyzed by FeCl3 at ambient temperature. Catalytic amounts of CuI salts, CpTiCl3, and [CpFe(CO) 2]2 are similarly effective. 2-Methylpropane, generated after quench of excess TIBA can be trapped, and excess dibromomethane can be recycled, which makes the method industrially applicable. Solvent-free DIBAH or TIBA reduction of unsaturated carbonyl compounds, followed by in situ TIBA cyclopropanation of the unsaturated aluminum alcoholates in dibromomethane give cyclopropyl alkanols. Dienols such as geraniol, linalool or nor-radjanol are selectively cyclopropanated in their distal position, which allows the synthesis of flavor and fragrance compounds such as δ-citral, cis-javanol, and 7-methyl-georgywood. Uncontrollable exothermic events are avoided due to relatively low reaction temperatures made possible by the catalysts and by the addition mode of the reagents.[1]
- Brunner, Gerhard,Elmer, Susanne,Schroeder, Fridtjof
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supporting information; experimental part
p. 4623 - 4633
(2011/10/09)
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- Termite trail attractants: New synthesis of racemic (E)-α-, (Z)-α- and β-bisabolenes
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Racemic (E)-α-bisabolene (E)(1) was synthetized starting from 4-methyl-3-cyclohexenecarboxylic acid (3) by a reaction sequence involving the Pd(0)-catalyzed cross-coupling reaction between the (E)-2-methyl-1-alkenyltrimethylstannane 8 and 3-methyl-2-buten-1-yl acetate (9). Three different procedures, in which a common precursor was used as key intermediate, were tested for the synthesis of racemic (Z)-α-bisabolene (Z)(1). The best one, which involved the reaction between bromide 18 and lithium dialkenylcuprate 19, afforded a mixture of (Z)- and (E)-1 in a 93:7 molar ratio, respectively. Finally, racemic β-bisabolene (2) was synthetized by a simple reaction sequence involving the Zr-promoted methylenation of ketone 22 prepared from 3.
- Argenti,Bellina,Carpita,Dell'Amico,Rossi
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p. 3167 - 3188
(2007/10/02)
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- Reductive Carbonylation of Alkenes using Zwitterionic Rhodium Complexes as Catalysts
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Alkenes react with carbon monoxide, sodium borohydride, propan-2-ol and a catalytic amount of Rh(cod)(η6-PhBPh3) (cod = cyclooctadiene) to give alcohols in fine yields; high regioselectivity for the branched or linear alcohol is usually observed, depending on the organic substrate.
- Zhou, Jian-Qiang,Alper, Howard
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p. 233 - 234
(2007/10/02)
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