Iron‐Catalyzed Generation of α‐Amino Nitriles from Tertiary Amines. Issue 14 (2nd October 2013)

• Record Type: Journal Article
• Authors: Wagner, Alexander; Han, Wei; Mayer, Peter; Ofial, Armin R.
• Is Part Of: Advanced synthesis & catalysis. Volume 355:Issue 14/15(2013)
• Page Start: 3058
• Page End: 3070
• Publication Date: 2013-10-02
• Subjects: Catalysis -- Periodicals; Organic compounds -- Synthesis -- Periodicals; Chemistry -- Periodicals; Chemistry, Technical -- Periodicals; Chemistry -- Periodicals; Catalysis -- Periodicals; Technology, Pharmaceutical -- Periodicals; 547.2
• DOI: 10.1002/adsc.201300441
• Languages: English
• ISSNs: 1615-4150

Abstract

<abstract abstract-type="main" xml:lang="en"> <title>Abstract</title> <p>The use of iron(II) chloride as catalyst, trimethylsilyl cyanide as source of cyanide ions, and <italic>tert</italic>‐butyl hydroperoxide as oxidant enabled the conversion of aromatic, benzylic, and aliphatic tertiary amines into α‐amino nitriles under mild conditions. Chemoselective functionalization of NCH₃ to NCH₂CN was achieved in the presence of <italic>N</italic>‐benzyl and <italic>N</italic>‐alkyl groups. <italic>N</italic>, <italic>N</italic>‐Dialkylanilines, PhNR₂, with R=Et, Bu, Bn furnished the alkyl(aryl)aminoacetonitriles PhN(R)CH₂CN as the main products accompanied by α‐amino nitriles generated by ordinary α‐cyanation of the aniline PhNR₂. Formation of PhN(R)CH₂CN was rationalized by oxidative degradation of <italic>N</italic>, <italic>N</italic>‐dialkylanilines to <italic>N</italic>‐alkylanilines, their condensation with formaldehyde, generated by oxidation of the solvent methanol, and final trapping of the thus formed iminium ions by cyanide.</p> <p> <boxed-text content-type="graphic" position="anchor" orientation="portrait"> <graphic position="anchor" mimetype="image" xlink:href="ark:/27927/pgg4t381vn6" orientation="portrait" xlink:type="simple" xmlns:xlink="http://www.w3.org/1999/xlink" /> </boxed-text> </p> </abstract>