Anilide activation of adjacent C-H bonds in the palladium-catalysed Fujiwara-Moritani reaction.
The Pd(II)-catalysed oxidative counterpart of the Heck reaction, originally described by Fujiwara and Moritani, has been studied in detail by a combination of NMR, single-crystal X-ray diffraction and substrate variation. The process involves a palladacycle that is a true intermediate in catalysis....
| Main Authors: | , , |
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| Format: | Journal article |
| Language: | English |
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2010
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| _version_ | 1826274639753510912 |
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| author | Rauf, W Thompson, A Brown, J |
| author_facet | Rauf, W Thompson, A Brown, J |
| author_sort | Rauf, W |
| collection | OXFORD |
| description | The Pd(II)-catalysed oxidative counterpart of the Heck reaction, originally described by Fujiwara and Moritani, has been studied in detail by a combination of NMR, single-crystal X-ray diffraction and substrate variation. The process involves a palladacycle that is a true intermediate in catalysis. Pd(OAc)(2) is first converted into a more electrophilic palladium species for effective catalysis, defining the main role of added acid. In the course of these studies, three palladacyclic intermediates have been characterised by X-ray diffraction, firstly the directly produced acetate complex 1, the camphorsulfonate complex 2, and additionally tosylate 3, isolated from a reacting system, demonstrating the accessibility of a cationic or comparably electrophilic palladium entity under turnover conditions. The isolated palladacycle 3 is also an effective catalyst. The reaction rate shows a first-order dependency on [anilide] and [Pd], but not on benzoquinone, alkene or p-TsOH. Acid, in the form of p-TsOH, is an essential component, whereas acetate is dispensable. A crossover experiment involving distinct substitution in reactant and palladacycle demonstrates that the palladacycle is directly involved in the catalysis. |
| first_indexed | 2024-03-06T22:46:30Z |
| format | Journal article |
| id | oxford-uuid:5d5bcf5a-2d86-4d87-ba9c-83914c91f89e |
| institution | University of Oxford |
| language | English |
| last_indexed | 2024-03-06T22:46:30Z |
| publishDate | 2010 |
| record_format | dspace |
| spelling | oxford-uuid:5d5bcf5a-2d86-4d87-ba9c-83914c91f89e2022-03-26T17:33:59ZAnilide activation of adjacent C-H bonds in the palladium-catalysed Fujiwara-Moritani reaction.Journal articlehttp://purl.org/coar/resource_type/c_dcae04bcuuid:5d5bcf5a-2d86-4d87-ba9c-83914c91f89eEnglishSymplectic Elements at Oxford2010Rauf, WThompson, ABrown, JThe Pd(II)-catalysed oxidative counterpart of the Heck reaction, originally described by Fujiwara and Moritani, has been studied in detail by a combination of NMR, single-crystal X-ray diffraction and substrate variation. The process involves a palladacycle that is a true intermediate in catalysis. Pd(OAc)(2) is first converted into a more electrophilic palladium species for effective catalysis, defining the main role of added acid. In the course of these studies, three palladacyclic intermediates have been characterised by X-ray diffraction, firstly the directly produced acetate complex 1, the camphorsulfonate complex 2, and additionally tosylate 3, isolated from a reacting system, demonstrating the accessibility of a cationic or comparably electrophilic palladium entity under turnover conditions. The isolated palladacycle 3 is also an effective catalyst. The reaction rate shows a first-order dependency on [anilide] and [Pd], but not on benzoquinone, alkene or p-TsOH. Acid, in the form of p-TsOH, is an essential component, whereas acetate is dispensable. A crossover experiment involving distinct substitution in reactant and palladacycle demonstrates that the palladacycle is directly involved in the catalysis. |
| spellingShingle | Rauf, W Thompson, A Brown, J Anilide activation of adjacent C-H bonds in the palladium-catalysed Fujiwara-Moritani reaction. |
| title | Anilide activation of adjacent C-H bonds in the palladium-catalysed Fujiwara-Moritani reaction. |
| title_full | Anilide activation of adjacent C-H bonds in the palladium-catalysed Fujiwara-Moritani reaction. |
| title_fullStr | Anilide activation of adjacent C-H bonds in the palladium-catalysed Fujiwara-Moritani reaction. |
| title_full_unstemmed | Anilide activation of adjacent C-H bonds in the palladium-catalysed Fujiwara-Moritani reaction. |
| title_short | Anilide activation of adjacent C-H bonds in the palladium-catalysed Fujiwara-Moritani reaction. |
| title_sort | anilide activation of adjacent c h bonds in the palladium catalysed fujiwara moritani reaction |
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