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A new synthesis of (±)‐phoracantholide, (±)‐dihydrorecifeiolide, and (±)‐muscone via α‐nitro ketones
Author(s) -
Ballini Roberto,
Marcantoni Enrico,
Petrini Marino
Publication year - 1995
Publication title -
liebigs annalen
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 0947-3440
DOI - 10.1002/jlac.1995199507185
Subject(s) - chemistry , nitro , medicinal chemistry , alkylation , ketone , benzene , organic chemistry , raney nickel , heptane , catalysis , alkyl
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.