Title |
Metal–Organic Frameworks Invert Molecular Reactivity: Lewis Acidic Phosphonium Zwitterions Catalyze the Aldol-Tishchenko Reaction
|
---|---|
Published in |
Journal of the American Chemical Society, December 2017
|
DOI | 10.1021/jacs.7b10928 |
Pubmed ID | |
Authors |
Gerald Bauer, Daniele Ongari, Xiaoying Xu, Davide Tiana, Berend Smit, Marco Ranocchiari |
Abstract |
The influence of metal-organic frameworks (MOFs) as additives is herein described for the reaction of n-alkyl aldehydes in the presence of methylvinylketone and tri-phenylphosphine. In the absence of a MOF, the expected Morita-Baylis-Hillman product - a β-hydroxy enone - is observed. In the presence of MOFs with UMCM-1 and MOF-5 topologies, the reaction is selective to Aldol-Tishchenko products - the 1 and 3 n-alkylesters of 2-alkyl-1,3-diols - that is unprecedented in organocatalysis. The (3-oxo-2-butenyl)triphenylphosphonium zwitterion, a commonly known nucleophile, is identified as the catalytic active species. This zwitterion favours nucleophilic character in solution, whereas once confined within the framework, it becomes an electrophile yielding Aldol-Tishchenko selectivity. Computational investigations reveal a structural change in the phosphonium moiety induced by the steric confinement of the framework that makes it accessible and an electrophile. |
X Demographics
Geographical breakdown
Country | Count | As % |
---|---|---|
United States | 2 | 33% |
Germany | 2 | 33% |
Unknown | 2 | 33% |
Demographic breakdown
Type | Count | As % |
---|---|---|
Scientists | 2 | 33% |
Members of the public | 2 | 33% |
Science communicators (journalists, bloggers, editors) | 1 | 17% |
Unknown | 1 | 17% |
Mendeley readers
Geographical breakdown
Country | Count | As % |
---|---|---|
Switzerland | 1 | 2% |
Unknown | 56 | 98% |
Demographic breakdown
Readers by professional status | Count | As % |
---|---|---|
Student > Ph. D. Student | 12 | 21% |
Researcher | 6 | 11% |
Student > Bachelor | 6 | 11% |
Student > Master | 5 | 9% |
Student > Doctoral Student | 4 | 7% |
Other | 12 | 21% |
Unknown | 12 | 21% |
Readers by discipline | Count | As % |
---|---|---|
Chemistry | 29 | 51% |
Chemical Engineering | 4 | 7% |
Physics and Astronomy | 3 | 5% |
Engineering | 2 | 4% |
Biochemistry, Genetics and Molecular Biology | 1 | 2% |
Other | 3 | 5% |
Unknown | 15 | 26% |