A one-pot, two step synthesis of 2,2-disubstituted 1-nitroalkenes

✍ Scribed by Yeong-Jiunn Jang; Wen-Wei Lin; Yuh-Kuo Shih; Ju-Tsung Liu; Ming-Hsing Hwang; Ching-Fa Yao

• Publisher: Elsevier Science
• Year: 2003
• Tongue: French
• Weight: 303 KB
• Volume: 59
• Category: Article
• ISSN: 0040-4020
• DOI: 10.1016/s0040-4020(03)00754-3

✦ Synopsis

The reactions of ketones 1a -o, nitromethane 2, and a stoichiometric amount of piperidine 3a or ethylenediamine 3b in the presence of mercaptan 6a in THF or CH 3 CN solution give high yields of b-nitrosulfides 7a -o. The latter can be oxidized by 8a (m-CPBA or m-CPBA/AcOH) at 08C, 8b (H 2 O 2 /AcOH), or 8c (H 2 O 2 ) at room temperature, thus generating b-nitroalkylsulfoxides 9a -o, which then undergo elimination to produce medium to high yields of 2,2-disubstituted-1-nitroalkenes 5a -o, when refluxed in a solution of ClCH 2 CH 2 Cl (1,2-dichloroethane). After preparation from 1a -o, 2, 3, and 6a, 7a -o were oxidized with 8a, 8b, or 8c in a mixture of CH 3 CN and ClCH 2 CH 2 Cl to generate b-nitrosulfoxides 9a -o, which then underwent elimination under refluxing under one-pot conditions. Compounds 14 and 15g were also prepared using 13, 2, 3b, and 6, in a similar manner.