Diastereoselective diazenyl formation: the key for manganese-catalysed alcohol conversion into (E)-alkenes

Type
Article

Authors
Azofra Mesa, Luis
Poater, Albert

Date
2019-09-04

Abstract
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.

Citation
Azofra, L. M., & Poater, A. (2019). Diastereoselective diazenyl formation: the key for manganese-catalysed alcohol conversion into (E)-alkenes. Dalton Transactions, 48(37), 14122–14127. doi:10.1039/c9dt03379c

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.

Publisher
Royal Society of Chemistry (RSC)

Journal
DALTON TRANSACTIONS

DOI
10.1039/c9dt03379c

Additional Links
http://xlink.rsc.org/?DOI=C9DT03379C

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