A Cyanide‐Free Synthesis of Acylcyanides through Ru‐Catalyzed C(sp3)‐H‐Oxidation of Benzylic Nitriles. Issue 6 (25th April 2019)

• Record Type: Journal Article
• Authors: Eisele, Pascal; Bauder, Michael; Hsu, Shih‐Fan; Plietker, Bernd
• Is Part Of: ChemistryOpen. Volume 8:Issue 6(2019)
• Page Start: 689
• Page End: 691
• Publication Date: 2019-04-25
• Subjects: acylcyanides -- oxidation reactions -- catalysis -- ruthenium -- cyanohydrines; Chemistry -- Periodicals; 540; 540.5
• DOI: 10.1002/open.201900130
• Languages: English
• ISSNs: 2191-1363

Abstract

Abstract: A practical method for generation of acylcyanides devoid of any external cyanide sources is presented that relies on a mild Ru‐catalyzed selective C−H‐oxidation of benzylic nitriles. The starting materials are smoothly generated through condensation of the corresponding carboxylic acid amides using silanes. The obtained acylcyanides can be employed in a plethora of transformation as exemplified to some larger extend in the sequence of C−H‐oxidation‐Tischenko‐rearrangement for the generation of structurally diverse benzoyloxycyanohydrines. Abstract : Three on one strike : The Ru‐catalyzed C−H‐oxidation of benzylnitrile derivatives provides access toward reactive acylcyanides which can be transformed in‐situ into esters, amides, but also into acylcyanohydrines. Upon coupling the process to a fluoride‐catalyzed dehydrogenation of carboxylic acid amides allows for a three‐step, one‐pot preparation of acylcyanohydrines without the need to employ cyanide salts.