- Ligand-Controlled Palladium-Catalyzed Alkoxycarbonylation of Allenes: Regioselective Synthesis of α,β- and β,γ-Unsaturated Esters
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The palladium-catalyzed regioselective alkoxycarbonylation of allenes with aliphatic alcohols allows to produce synthetically useful α,β- and β,γ-unsaturated esters in good yields. Efficient selectivity control is achieved in the presence of appropriate ligands. Using Xantphos as the ligand, β,γ-unsaturated esters are produced selectively in good yields. In contrast, the corresponding α,β-unsaturated esters are obtained with high regioselectivity in the presence of PPh2Py as the ligand. Preliminary mechanistic studies revealed that these two catalytic processes proceed by different reaction pathways. In addition, this novel protocol was successfully applied to convert an industrially available bulk chemical, 1,2-butadiene, into dimethyl adipate, which is a valuable feedstock for polymer and plasticizer syntheses, with high yield and TON (turnover number).
- Liu, Jie,Liu, Qiang,Franke, Robert,Jackstell, Ralf,Beller, Matthias
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supporting information
p. 8556 - 8563
(2015/07/15)
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- Undirected arene and chelate-assisted olefin C-H bond activation: [Rh IIICp*]-catalyzed dehydrogenative alkene-arene coupling as a new pathway for the selective synthesis of highly substituted Z olefins
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Undirected/Directed Cross-Coupling: A new dehydrogenative Rh III-catalyzed cross-coupling reaction between bromoarenes bearing no directing group and vinylic substrates substituted by a chelating group is reported. An original reaction mechanism enables the use of internal alkenes in a Z-selective coupling. The application of 1,3-disubstituted or 1,2-homodisubstituted arenes leads to the formation of highly functionalized, complex, and valuable olefins as one single isomer. Copyright
- Wencel-Delord, Joanna,Nimphius, Corinna,Patureau, Frederic W.,Glorius, Frank
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supporting information; experimental part
p. 1208 - 1212
(2012/07/28)
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- ENZYMATIC ENANTIOSELECTIVE HYDROLYSIS OF 2,2-DIMETHYL-1,3-DIOXOLANE-4-CARBOXYLIC ESTERS
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2,2-dimethyl-1,3-dioxolane-4-carboxylic acid derived chiral building blocks were prepared from substituted α,β-unsaturated acids with high enantiomeric purities by enzymatic hydrolysis of their n.butyl esters.
- Pottie, M.,Eycken, J. Van der,Vandewalle, M.,Dewanckele, J. M.,Roeper, H.
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p. 5319 - 5322
(2007/10/02)
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