(NHC)Pd(II) hydride-catalyzed dehydroaromatization by olefin chain-walking isomerization and transfer-dehydrogenation

Weihao Chen, Yang Chen, Xiao Gu, Zaizhu Chen and Chun-Yu Ho ()
Additional contact information
Weihao Chen: Southern University of Science and Technology (SUSTech)
Yang Chen: Southern University of Science and Technology (SUSTech)
Xiao Gu: Southern University of Science and Technology (SUSTech)
Zaizhu Chen: Southern University of Science and Technology (SUSTech)
Chun-Yu Ho: Southern University of Science and Technology (SUSTech)

Nature Communications, 2022, vol. 13, issue 1, 1-11

Abstract: Abstract Transition-metal-catalyzed homogeneous dehydrogenation and isomerization are common organic molecular activation reactions. Palladium hydrides are good olefin isomerization catalysts but are usually short-lived species under redox-active dehydrogenation conditions. Here, we show that Pd-H in the presence of an N-heterocyclic carbene ligand and an alkene regulator enables transfer-dehydroaromatization, avoiding the homo-disproportionation pathway. The desired product is obtained with up to 99:1 selectivity, and the exo-to-endo olefin isomerization can be carried out in one pot. In contrast to previously reported methods that rely on the efficient removal of Pd-H, the approach reported herein benefits from the steric effects of the N-heterocyclic carbene and the choice of alkene to regulate the competing reactivity of allylic C‒H activation and hydropalladation. This method circumvents the challenges associated with tedious olefin separation and a low exo-to-endo olefin isomerization ratio and expands the scope to include challenging endo- and exo-cyclic olefins under mild, neutral, and oxidant-free conditions. Overall, herein, we provide a strategy to synthesize (hetero)aromatic compounds via chemoselective dehydrogenation of cyclic alkenes over ketones and the dehydrogenative Diels-Alder reaction of a cyclic enamine.

Date: 2022
References: View complete reference list from CitEc
Citations:

Downloads: (external link)
https://www.nature.com/articles/s41467-022-33163-6 Abstract (text/html)

Related works:
This item may be available elsewhere in EconPapers: Search for items with the same title.

Export reference: BibTeX RIS (EndNote, ProCite, RefMan) HTML/Text

Persistent link: https://EconPapers.repec.org/RePEc:nat:natcom:v:13:y:2022:i:1:d:10.1038_s41467-022-33163-6

Ordering information: This journal article can be ordered from
https://www.nature.com/ncomms/

DOI: 10.1038/s41467-022-33163-6

Access Statistics for this article

Nature Communications is currently edited by Nathalie Le Bot, Enda Bergin and Fiona Gillespie

More articles in Nature Communications from Nature
Bibliographic data for series maintained by Sonal Shukla () and Springer Nature Abstracting and Indexing ().