康 · 学术 | Reaction of the Day No. 1760

Mild Heterogeneous Thiophene Hydrogenation Enabled by a Modified Palladium Catalyst

Steffen Heuvel, Marie-Christin Leusmann, Julius Wiener, Arne Nalop, Bonnie J. Tyler, Mathis J. Karrasch, and Frank Glorius*

Center for Soft Nanoscience, University of Münster, Busso-Peus-Stra?e 10, 48149 Münster, Germany;

PhysikalischesInstitut, University of Münster, Wilhelm- Klemm-Stra?e 10, 48149 Münster, Germany;

Organisch-ChemischesInstitut, University of Münster, Corrensstra?e 36, 48149 Münster, Germany;

International Graduate School for Battery Chemistry, Characterization, Analysis, Recycling and Application (BACCARA), 

University of Münster, Corrensstra?e 40, 48149 Münster, Germany.

—ACS Catal., 2026, DOI: https://doi.org/10.1021/acscatal.6c06048

Recommended by Yuting Gao_ MC3

KEY WORDS: thiophene hydrogenation, Pd catalysis (反应类型),thiolanes (原料), tetrahydrothiophenes, saturated sulfur heterocycles (产物), Pd(OH)2/C, CHCl3 (其他).

ABSTRACT: The group of Pro. Frank Glorius reported a chloroform-induced surface modification strategy that enables the heterogeneous Pd(OH)2/C-catalyzed hydrogenation of thiophenes to saturated sulfur heterocycles. The method proceeds under mild hydrogenation conditions and provides access to a range of alkyl-, silyl-, aryl-, and benzofusedthiolane derivatives. A hydrogenation-focused robustness assessment revealed compatibility with several functional groups that are commonly sensitive under Pd/H2 conditions, while preparative scope studies showed that functional-group-containing thiophenes can be converted when potentially interfering motifs are separated from the thiophene core by suitable alkyl or aryl spacers.

Background & Work Design

Conditions Optimization

Selected examples of functional group compatibility and robustness assessment. 

(A)Compatible additives: high product yield (65–100%) and high additive recovery (65–100%).  (B)Converted additives: high product yield (65–100%) but low additive recovery (0–29%). (C)Inhibitory additives: Substantial inhibition of product formation. 

The histograms show the distributions of product yields and additive recoveries across the robustness screen; N denotes the number of additives within the respective interval, and the gray line indicates the mean value.

Substrates Scope

Control Experiments

Summary and Comments

The group of Pro. Frank Glorius have developed a heterogeneous Pd-catalyzed hydrogenation of thiophenes that enables direct access to saturated sulfur heterocycles while preserving the thiolane framework. The method proceeds under mild hydrogenation conditions and can be applied to a range of substituted thiophenes, including alkyl-, silyl-, aryl-, and benzofused derivatives. Importantly, the preparative scope also demonstrates that functional-group-containing thiophenes can be converted when potentially interfering motifs are separated from the heteroaromatic core by suitable alkyl or aryl spacers. This spacer dependence provides a practical link between the hydrogenation-focused robustness assessment and substrate design, showing that several functional groups commonly considered sensitive under Pd/H2 conditions can be accommodated without preventing thiophene saturation. At the same time, directly attached polar functionalities, strongly coordinating groups, and catalyst-poisoning motifs remain clear limitations of the method.