Reactions of methylcubane (1) with the tert-butoxyl radical (t-BuO • ), with cytochrome P-450 enzymes, and with a methane monooxygenase (MMO) system have been studied. For the purpose of product characterization, authentic samples of 2-methylcubyl and 4-methylcubyl derivatives were prepared. 2-Methylcubanecarboxylic acid (9b) is a new compound prepared from cubanecarboxylic acid. The key synthetic reactions were (1) metalation and subsequent iodination of the 2-position of (diisopropylcarbamoyl)cubane to effect the initial functionalization, (2) lithium-for-iodine exchange and methylation followed by reduction to give 2-methyl-1-[(diisopropylamino)methyl]cubane, and (3) dimethyldioxirane oxidation of this amine to give 9b. The known 4-methylcubanecarboxylic acid (9d) was prepared here by a route related to that employed for 9b. Reactions of acids 9b and 9d with methyllithium gave the corresponding methyl ketones which were oxidized by m-chloroperoxybenzoic acid to provide authentic samples of 2-and 4-methylcubanol acetates (3b and 3d). Reaction of 1 with t-BuO • in the presence of 2,2,5,5tetramethylisoindole-N-oxyl radical (TMIO • ) at 40-55 °C gave mainly cube-substituted products in confirmation of the report (

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Details for preparation of 1,4-diiodocubane from cubane-l,4-dicarboxylic acid are given. The diiodide is used to generate cubane-1,4-diyl, a nonisolable intermediate. Additions to the diyl are shown to provide for the ready synthesis in good yield of methylcubane, 1,4-dimethylcubane, cyclopropylcubane, etc.

A series of 1,3‐bis(1H‐azol‐1‐yl)‐2‐aryl‐2‐propanols 17 were synthesized in an one‐pot procedure by reacting l‐aryl‐2‐(1H‐1,2,4‐triazol‐l‐yl)‐ or l‐aryl‐2‐(1H‐imidazol‐l‐yl)ethanones with dimethylsulfoxonium methide in the presence of either 1,2,4‐triazole or imidazole. The aromatic groups in 17 were either 4‐bromo‐, 4‐chloro‐, 2,4‐dichloro‐ or 2,4‐difluorophenyl. 4‐Amino‐4H‐1,2,4‐triazole was acylated with either benzoyl or 4‐toluene‐sulfonyl chloride to afford [4‐(benzoyl or 4‐toluenesulfonyl)amino]4H‐1,2,4‐triazole. Subsequent alkylations with 4‐bromo‐ or 4‐chlorophenacyl bromide produced 1‐(4‐bromo‐ or 4‐chlorophenacyl)‐4‐[(benzoyl‐ or 4‐toluenesulfonyl)amino]‐1H‐1,2,4‐triazolium bromides. Neutralizations of these salts provided the corresponding ylides.

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