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

Chen，Weihao1,2,3; Chen，Yang1,2,3; Gu，Xiao1,2,3; Chen，Zaizhu1,3; Ho，Chun Yu1,2,3

2022-12-01

10.1038/s41467-022-33163-6

Nature Communications   Impact Factor & Quartile

2041-1723

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.

SCI

English

NI Journal Papers ; NI论文

First

National Natural Science Foundation of China-Yunnan Joint Fund[22071096];

Science & Technology - Other Topics

Multidisciplinary Sciences

WOS:000856140700027

NATURE PORTFOLIO

2-s2.0-85138192654

Scopus

1.Guangdong Provincial Key Laboratory of Catalysis,Southern University of Science and Technology (SUSTech),Shenzhen,China
2.Shenzhen Grubbs Institute,Department of Chemistry,Southern University of Science and Technology (SUSTech),Shenzhen,China
3.Department of Chemistry,Southern University of Science and Technology (SUSTech),Shenzhen,China

Chen，Weihao,Chen，Yang,Gu，Xiao,et al. (NHC)Pd(II) hydride-catalyzed dehydroaromatization by olefin chain-walking isomerization and transfer-dehydrogenation[J]. Nature Communications,2022,13(1).

Chen，Weihao,Chen，Yang,Gu，Xiao,Chen，Zaizhu,&Ho，Chun Yu.(2022).(NHC)Pd(II) hydride-catalyzed dehydroaromatization by olefin chain-walking isomerization and transfer-dehydrogenation.Nature Communications,13(1).

Chen，Weihao,et al."(NHC)Pd(II) hydride-catalyzed dehydroaromatization by olefin chain-walking isomerization and transfer-dehydrogenation".Nature Communications 13.1(2022).