The proposed reaction mechanism for the unprecedented direct transformation of primary alcohols into alkenes catalysed by Mn(I)-PNP complexes consists of two cycles. First, the acceptorless dehydrogenation of the alcohol into aldehyde is produced via a concerted mechanism. Secondly, in an excess of hydrazine, hydrazone is formed and reacts with the aldehyde to produce olefins. This process, taking place in base-free conditions, is characterised by the diastereoselective formation of diazenyl intermediates. Based on DFT data, the generation of the (SN,S,S) diastereoisomer is favoured over the rest, leading in its decomposition to the preferential formation of an (E)-alkene and liberating N2 and H2O as the only by-products.
|Original language||English (US)|
|Number of pages||6|
|State||Published - Sep 4 2019|
Bibliographical noteKAUST Repository Item: Exported on 2022-06-07
Acknowledgements: L. M. A. is an ULPGC Postdoc Fellow, and thanks Universidad de Las Palmas de Gran Canaria (ULPGC). A. P. is a Serra Húnter Fellow, and thanks the Ministerio de Ciencia, Innovación y Universidades (MICINN) for project PGC2018-097722-B-I00. We also acknowledge the KAUST Supercomputing Laboratory, using the supercomputer Shaheen II, for providing the computational resources.
This publication acknowledges KAUST support, but has no KAUST affiliated authors.
ASJC Scopus subject areas
- Inorganic Chemistry