Zwitterionic Acridinium Amidate for Photocatalytic Acceptorless Dehydrogenation

Soichiro Mori; Lukas-Maximilian Entgelmeier; Yaoki Kansaku; Duc An Truong; Olga García Mancheño; Kohsuke Ohmatsu; Takashi Ooi

doi:10.1055/a-2596-9970

Synlett, Table of Contents

Synlett
DOI: 10.1055/a-2596-9970

letter

Hydrogen Atom Transfer Reactions

Zwitterionic Acridinium Amidate for Photocatalytic Acceptorless Dehydrogenation

Soichiro Mori‡

^aInstitute of Transformative Bio-Molecules (WPI-ITbM), and Department of Molecular and Macromolecular Chemistry, Graduate School of Engineering, Nagoya University, Nagoya 464-8601, Japan

,

Lukas-Maximilian Entgelmeier‡

^bOrganic Chemistry Institute, University of Münster, 48149 Münster, Germany

,

Yaoki Kansaku

^aInstitute of Transformative Bio-Molecules (WPI-ITbM), and Department of Molecular and Macromolecular Chemistry, Graduate School of Engineering, Nagoya University, Nagoya 464-8601, Japan

,

Duc An Truong

^aInstitute of Transformative Bio-Molecules (WPI-ITbM), and Department of Molecular and Macromolecular Chemistry, Graduate School of Engineering, Nagoya University, Nagoya 464-8601, Japan

,

Olga García Mancheño∗

^bOrganic Chemistry Institute, University of Münster, 48149 Münster, Germany

,

Kohsuke Ohmatsu∗

^cDepartment of Chemistry, Faculty of Science and Technology, Keio University, Yokohama 223-8522, Japan

,

Takashi Ooi∗

^aInstitute of Transformative Bio-Molecules (WPI-ITbM), and Department of Molecular and Macromolecular Chemistry, Graduate School of Engineering, Nagoya University, Nagoya 464-8601, Japan

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Abstract

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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 - aromatization

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References

References and Notes
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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%)].

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