Nitromethane anions, nucleophilic substitution

Ozonolysis of the alkene frees the carboxylic acid, which reacts with carbonyl diimidazole (GDI) n a nucleophilic substitution at the carbonyl group. The relatively stable imidazole anion is the ea ing group. The anion of nitromethane displaces the second imidazole anion and completes the uence. 

Bowman has surveyed the reactions of cx-substituted aliphatic nitro compounds with nucleophiles, which undergo either S l substitution or polar reaction (Scheme 5.16).118 The reactions between a wide variety of nucleophiles and BrCH2N02 are shown in Scheme 5.17.119a b All the thiolates, PhS02 and I attack Br to liberate the anion of nitromethane. The hard nucleophiles, MeO , OH, and BH4 attack the hard H+ electrophilic center. Phosphorous nucleophiles attackthe oxygen electrophilic center, and only Me2S attacks the carbon electrophilic center. 

Photostimulated, S r k 1 reactions of carbanion nucleophiles in DMSO have been used to advantage in C—C bond formation (Scheme 1).25-27 Thus, good yields of substitution products have been obtained from neopentyl iodide on reaction with enolates of acetophenone and anthrone, but not with the conjugate base of acetone or nitromethane (unless used in conjunction, whereby the former acts as an entrainment agent).25 1,3-Diiodoadamantane forms an intermediate 1-iodo mono substitution product on reaction with potassium enolates of acetophenone and pinacolone and with the anion of nitromethane subsequent fragmentation of the intermediate gives derivatives of 7-methylidenebicyclo[3.3.1]nonene. Reactions of 1,3-dibromo- and 1-bromo-3-chloro-adamantane are less effective.26... 

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