Synthesis of Indolones via Radical Cyclization of N-(2-Halogenoalkanoyl)-Substituted Anilines

✍ Scribed by Takehiko Nishio; Kyoko Iseki; Norihito Araki; Takenori Miyazaki

• Publisher: John Wiley and Sons
• Year: 2005
• Tongue: German
• Weight: 80 KB
• Volume: 88
• Category: Article
• ISSN: 0018-019X
• DOI: 10.1002/hlca.200490294

✦ Synopsis

Abstract

The radical reactions of N‐(2‐halogenoalkanoyl)‐substituted anilines (anilides) of type 1 have been investigated under various conditions. Treatment of compounds 1a–1o with Bu~3~SnH in the presence of (2,2′‐azobis(isobutyronitrile) (AIBN) afforded a mixture of the indolones (oxindoles) 2a–2o and the reduction products 5a–5o (Table 1). In contrast, the N‐unsubstituted anilides 1p–1s, 1u, and 1v gave the corresponding reduction products exclusively (Table 1). Similar results were obtained by treatment of 1 with Ni powder (Table 2) or wth Et~3~B (Table 3). Anilides with longer N‐(phenylalkyl) chains such as 6 and 7 were inert towards radical cyclization, with the exception of N‐benzyl‐2‐bromo‐N,2‐dimethylpropanamide (6b), which, upon treatment with Ni powder in i‐PrOH, afforded the cyclized product 9b in low yield (Table 4). Upon irradiation, the extended anilides 6, 7, 10, and 11 yielded the corresponding dehydrobromination products exclusively (Table 5).