A new synthesis of (±)-phoracantholide, (±)-dihydrorecifeiolide, and (±)-muscone via α-nitro ketones

✍ Scribed by Ballini, Roberto ;Marcantoni, Enrico ;Petrini, Marino

• Publisher: John Wiley and Sons
• Year: 1995
• Tongue: English
• Weight: 317 KB
• Volume: 1995
• Category: Article
• ISSN: 0947-3440
• DOI: 10.1002/jlac.1995199507185

✦ Synopsis

Abstract

C~α′~ alkylation of α‐nitro cycloalkanones 1a–c with methyl iodide at −35 to −70°C in THF/heptane/DMPU/TMDA in the presence of LDA as a base furnished the methylated α‐nitro ketones 2a–c. Denitration of 2a, b with Bu~3~SnH/AIBN in dry benzene afforded the α′‐methylated ketones 3a, b, which were converted to (±)‐phoracantholide (4a) and (±)‐dihydrorecifeiolide (4b), respectively, by the Baeyer‐Villiger oxidation. Reduction of 2c with NaBH~4~ and dehydration of the obtained nitro alkanol 5 with Al~2~O~3~/DMAP furnished the corresponding nitro alkene 6. Nef conversion of 6 with sodium hypophosphite and Raney nickel afforded (±)‐muscone (7) in good yields.