Selective palladium-catalyzed dehydrogenation of limonene to dimethylstyrene
Conditions for the selective dehydrogenation of (+)-limonene 1 to the polymer building block dimethylstyrene 2 are described. The reaction occurs smoothly in the presence of Pd(OTFA)2 as catalyst and CuCl2 as oxidant. High selectivity for retaining the exocyclic double bond during aromatization is a...
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| Main Authors: | , , |
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| Format: | Article (Journal) |
| Language: | English |
| Published: |
[February 8, 2010]
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| In: |
ChemCatChem
Year: 2010, Volume: 2, Issue: 2, Pages: 175-181 |
| ISSN: | 1867-3899 |
| DOI: | 10.1002/cctc.200900200 |
| Online Access: | Verlag, lizenzpflichtig, Volltext: https://doi.org/10.1002/cctc.200900200 Verlag, lizenzpflichtig, Volltext: https://onlinelibrary.wiley.com/doi/abs/10.1002/cctc.200900200 
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| Author Notes: | Patricia Horrillo-Martínez, Marie-Alice Virolleaud, and Christoph Jaekel |
| Summary: | Conditions for the selective dehydrogenation of (+)-limonene 1 to the polymer building block dimethylstyrene 2 are described. The reaction occurs smoothly in the presence of Pd(OTFA)2 as catalyst and CuCl2 as oxidant. High selectivity for retaining the exocyclic double bond during aromatization is achieved (>14:1). Initially, variable-temperature NMR experiments, under stoichiometric conditions, showed a stepwise formation of a π-allyl intermediate and subsequent reaction to give a mixture of products. However, kinetic experiments showed a sigmoidal curve, pointing to the heterogeneous nature of the catalytically active species. A number of experiments were undertaken to differentiate between homogeneous, molecularly defined catalysis and heterogeneous, nanocluster-based catalysis. Based on the results, it is proposed that the true catalytic system is heterogeneous in nature. |
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| Item Description: | First published: 01 February 2010 Gesehen am 17.04.2023 |
| Physical Description: | Online Resource |
| ISSN: | 1867-3899 |
| DOI: | 10.1002/cctc.200900200 |