A method for preparing trihydroxybutyl analogues of the biologically active compound 2-acetyl-4(5)-( 1,2,3,4-tetrahydroxybutyl)imidazole (THI) is reported. This method employs a palladium(O)catalyzed coupling of l-(ethoxymethyl)-4-iodoimidazole (3a) to functionalized vinylstannane 11, 1-alkynylstannane 16, or alkyne 10 to introduce the C-4 imidazole 4-carbon side chain. The 1,2dihydroxyfunctionality of the butyl side chain was introduced by a Sharpless catalytic asymmetric
An alternative synthesis of the insensitive energetic nitramine 2-nitroimino-5-nitrohexahydro-1,3,5-triazine (1) via nitrolysis of a tertiary amine is presented. Nitration of the tertiary amine precursor (2) is effected by chloride-assisted elimination of the tert-butyl moiety, with the chloramine presumably formed as an intermediate. The reaction fails to proceed in the absence of chloride at 0 C, however, its inclusion in the reaction system leads to a smooth conversion to (1) under mild nitrating conditions, which can be scaled up to yield multigram quantities. This is the ®rst known example of a chlorideassisted nitrolysis of a tertiary amine to appear in the open literature.
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