Aromatic Allylation via Diazotization:  Metal-Free C−C Bond Formation

• Published in: Journal of organic chemistry Vol. 67; no. 18; pp. 6376 - 6381
• Main Authors: Ek, Fredrik, Axelsson, Oskar, Wistrand, Lars-Göran, Frejd, Torbjörn
• Format: Journal Article
• Language: English
• Published: WASHINGTON American Chemical Society 06.09.2002; Amer Chemical Soc
• Subjects: Chemical Sciences; Chemistry; Chemistry, Organic; Exact sciences and technology; Kemi; Natural Sciences; Naturvetenskap; Noncondensed benzenic compounds; Organic Chemistry; Organisk kemi; Physical Sciences; Preparations and properties; Science & Technology; ALKYL NITRITES; HYDROGEN; CROSS-COUPLING REACTIONS; DEAMINATION; REAGENTS; RELATIVE REACTIVITIES; PHENYL RADICALS; ARYL RADICALS; ATOM ABSTRACTION; ARYLAMINES; Regioselectivity; Aniline derivatives; Allylic compound; Allylation; Diazotization; Amine; Deamination; Acetonitrile; Reaction mechanism; Bromine Organic compounds; Aromatic compound; Chemical synthesis; Organic nitrite
• ISSN: 0022-3263; 1520-6904; 1520-6904
• DOI: 10.1021/jo0258103

A new method for the synthesis of allyl aromatic compounds not involving any metal-containing reagent or catalyst has been developed. Arylamines substituted with a large number of different substituents were converted via diazotizative deamination with tert-butyl nitrite in allyl bromide and acetonitrile to the corresponding allyl aromatic compounds. The allylation reaction was found to be suitable for larger scale synthesis due to short reaction times, a nonextractive workup, and robustness toward moisture, air, and type of solvent.