Narobe, Rok and Murugesan, Kathiravan and Schmid, Simon and Koenig, Burkhard (2022) Decarboxylative Ritter-Type Amination by Cooperative Iodine (I/III)-Boron Lewis Acid Catalysis. ACS CATALYSIS, 12 (1). pp. 809-817. ISSN 2155-5435
Full text not available from this repository. (Request a copy)Abstract
Recent years have witnessed important progress in synthetic strategies exploiting the reactivity of carbocations via photochemical or electrochemical methods. Yet, most of the developed methods are limited in their scope to certain stabilized positions in molecules. Herein, we report a metal-free system based on the iodine (I/III) catalytic manifold, which gives access to carbenium ion intermediates also on electronically disfavored benzylic positions. The unusually high reactivity of the system stems from a complexation of iodine (III) intermediates with BF3. The synthetic utility of our decarboxylative Ritter-type amination protocol has been demonstrated by the functionalization of benzylic as well as aliphatic carboxylic acids, including late-stage modification of different pharmaceutical molecules. Notably, the amination of ketoprofen was performed on a gram scale. Detailed mechanistic investigations by kinetic analysis and control experiments suggest two mechanistic pathways.
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | IN-SITU; HYPERVALENT; REAGENTS; GENERATION; CHEMISTRY; TERTIARY; ACETOXYLATION; ALKYLATION; OXIDATION; ALKENES; amination; carbocations; iodine catalysis; photochemistry; Ritter reaction |
| Subjects: | 500 Science > 540 Chemistry & allied sciences |
| Divisions: | Chemistry and Pharmacy > Institut für Organische Chemie > Lehrstuhl Prof. Dr. Burkhard König |
| Depositing User: | Dr. Gernot Deinzer |
| Date Deposited: | 28 Jul 2022 08:15 |
| Last Modified: | 28 Jul 2022 08:15 |
| URI: | https://pred.uni-regensburg.de/id/eprint/46106 |
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