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Synlett 2025; 36(12): 1739-1742
DOI: 10.1055/a-2596-9970
DOI: 10.1055/a-2596-9970
letter
Hydrogen Atom Transfer Reactions
Zwitterionic Acridinium Amidate for Photocatalytic Acceptorless Dehydrogenation
This work was financially supported by MEXT KAKENHI Grants JP23H04901 and JP23H04907 (Green Catalysis Science); JSPS KAKENHI Grants 24K01481, 23H00296, and 22K21346; and JST FOREST Grant JPMJFR221L. The Deutsche Forschungsgemeinschaft (DFG, German Research Foundation) within the IRTG 2678–Functional π-Systems (pi-Sys) (Münster-Nagoya International Research Training Group, GRK 2678-437785492) and grant GA 1594-6/2 are also gratefully acknowledged for generous financial support.
Abstract
The development of catalytic systems that facilitate simple yet valuable molecular transformations in a sustainable manner is of fundamental importance in the field of synthetic organic chemistry. Herein, we report the expedient application of a zwitterionic acridinium amidate, a recently developed direct hydrogen-atom-transfer catalyst, in catalytic acceptorless dehydrogenation (CAD). The combined use of the acridinium amidate with a cobaloxime complex and a protic additive as a catalyst system enables the CAD of hydrocarbons to proceed with high efficiency under mild reaction conditions.
Key word
acceptorless dehydrogenation - photocatalysis - zwitterions - hybrid catalysis - dehydrogenation - aromatizationSupporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/a-2596-9970.
- Supporting Information
Publication History
Received: 11 March 2025
Accepted after revision: 29 April 2025
Accepted Manuscript online:
29 April 2025
Article published online:
10 June 2025
© 2025. Thieme. All rights reserved
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- 24 Acceptorless Dehydrogenation of 1,2,3,4-Tetrahydronaphthalene; Typical Procedure A flame-dried Schlenk tube equipped with a stirrer bar was charged with acridinium amidate 1 (1.6 mg, 0.003 mmol, 3 mol %), Co complex 2a (2.1 mg, 0.005 mmol, 5 mol %), and 2,4,6-collidinium tosylate (14.7 mg, 0.05 mmol). The tube was sealed with a rubber septum, evacuated, and backfilled with Ar five times, then DCE (500 μL) and 1,2,3,4-tetrahydronaphthalene (13.2 mg, 0.1 mmol, 1.0 equiv) were successively introduced into the Schlenk tube. The rubber septum was replaced with a glass stopper under a steady flow of Ar, and the tube was quickly evacuated and backfilled with Ar five times. The mixture was then stirred for 48 h under irradiation by two Kessil H150 Blue lamps, with fan cooling to maintain the temperature below 40 °C. The mixture was concentrated, and the yield of naphthalene was determined by GC-FID with 1,3,5-trimethoxybenzene as an internal standard [yield: 0.080 mmol (80%)].