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Alkene Transfer Hydrogenation with Alkaline‐Earth Metal Catalysts.
- Source :
-
Angewandte Chemie International Edition . 3/22/2019, Vol. 58 Issue 13, p4248-4253. 6p. - Publication Year :
- 2019
-
Abstract
- The alkene transfer hydrogenation (TH) of a variety of alkenes has been achieved with simple AeN′′2 catalysts [Ae=Ca, Sr, Ba; N′′=N(SiMe3)2] using 1,4‐cyclohexadiene (1,4‐CHD) as a H source. Reaction of 1,4‐CHD with AeN′′2 gave benzene, N′′H, and the metal hydride species N′′AeH (or aggregates thereof), which is a catalyst for alkene hydrogenation. BaN′′2 is by far the most active catalyst. Hydrogenation of activated C=C bonds (e.g. styrene) proceeded at room temperature without polymer formation. Unactivated (isolated) C=C bonds (e.g. 1‐hexene) needed a higher temperature (120 °C) but proceeded without double‐bond isomerization. The ligands fully control the course of the catalytic reaction, which can be: 1) alkene TH, 2) 1,4‐CHD dehydrogenation, or 3) alkene polymerization. DFT calculations support formation of a metal hydride species by deprotonation of 1,4‐CHD followed by H transfer. Convenient access to larger quantities of BaN′′2, its high activity and selectivity, and the many advantages of TH make this a simple but attractive procedure for alkene hydrogenation. The hydrogen shuffle: Transfer of hydrogens from 1,4‐cyclohexadiene to a variety of alkenes is catalyzed by simple alkaline‐earth metal amides. The proposed mechanism for this convenient and highly selective transfer hydrogenation is supported by DFT calculations. [ABSTRACT FROM AUTHOR]
- Subjects :
- *TRANSFER hydrogenation
*DEHYDROGENATION
*METAL catalysts
Subjects
Details
- Language :
- English
- ISSN :
- 14337851
- Volume :
- 58
- Issue :
- 13
- Database :
- Academic Search Index
- Journal :
- Angewandte Chemie International Edition
- Publication Type :
- Academic Journal
- Accession number :
- 135344397
- Full Text :
- https://doi.org/10.1002/anie.201813910