Please use this identifier to cite or link to this item:
doi:10.22028/D291-40174
Title: | Evidence for Carbene Intermediates in Isocyanide Homologation by Aluminium(I) |
Author(s): | Zhang, Cuijuan Dankert, Fabian Jiang, Ziang Wang, Baolu Munz, Dominik Chu, Jiaxiang |
Language: | English |
Title: | Angewandte Chemie : International Edition |
Volume: | 62 |
Issue: | 34 |
Publisher/Platform: | Wiley |
Year of Publication: | 2023 |
Free key words: | Aluminum Carbene Fischer–Tropsch Homologation Isocyanide |
DDC notations: | 540 Chemistry |
Publikation type: | Journal Article |
Abstract: | The C-C bond formation between C1 molecules plays an important role in chemistry as manifested by the Fischer-Tropsch (FT) process. Serving as models for the FT process, we report here the reactions between a neutral AlI complex (Me NacNac)Al (1, Me NacNac=HC[(CMe)(NDipp)]2 , Dipp=2,6-diisopropylphenyl) and various isocyanides. The step-by-step coupling mechanism was studied in detail by low-temperature NMR monitoring, isotopic labeling, as well as quantum chemical calculations. Three different products were isolated in reaction of 1 with the sterically encumbered 2,6-bis(benzhydryl)-4-Me-phenyl isocyanide (BhpNC). These products substantiate carbene intermediates. The reaction between 1 and adamantyl isocyanide (AdNC) generated a trimerization product, and a corresponding carbene intermediate could be trapped in the form of a molybdenum(0) complex. Tri-, tetra-, and even pentamerization products were isolated with the sterically less congested phenyl and p-methoxyphenyl isocyanides (PhNC and PMPNC) with concurrent construction of quinoline or indole heterocycles. Overall, this study provides evidence for carbene intermediates in FT-type chemistry of aluminium(I) and isocyanides. |
DOI of the first publication: | 10.1002/anie.202307352 |
URL of the first publication: | https://onlinelibrary.wiley.com/doi/10.1002/anie.202307352 |
Link to this record: | urn:nbn:de:bsz:291--ds-401742 hdl:20.500.11880/36152 http://dx.doi.org/10.22028/D291-40174 |
ISSN: | 1521-3773 |
Date of registration: | 24-Jul-2023 |
EU-Projectnumber: | info:eu-repo/grantAgreement/EC/ERC/948185/EU//PUSH-IT |
Faculty: | NT - Naturwissenschaftlich- Technische Fakultät |
Department: | NT - Chemie |
Professorship: | NT - Prof. Dr. Dominik Munz |
Collections: | SciDok - Der Wissenschaftsserver der Universität des Saarlandes |
Files for this record:
File | Description | Size | Format | |
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Angew Chem Int Ed - 2023 - Zhang - Evidence for Carbene Intermediates in Isocyanide Homologation by Aluminium I.pdf | 1,59 MB | Adobe PDF | View/Open |
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