cine - and tele -Substitution reactions

cine- and tele-Substitution reactions: review of work from 2002-2016

“…A long review, titled "Transition-MetalMediated Dearomatization Reactions" 2 , that appeared two years later only briefly mentioned cine-and telesubstitutions in arenetricarbonylchromium complexes, noting that both reactions probably involved the following sequence of reactions: nucleophilic addition, protonation, isomerization and elimination to reconstruct aromatic system (4 references). In 2001, we published the first general review article 3 on the cineand tele-substitutions describing these types of reactions in homoarenes, heteroarenes and aliphatic systems, regardless of nucleophilic, electrophilic or radical mechanisms of the reactions (210 references). One year later, Rose-Munch and Rose published a microreview on cine and tele nucleophilic substitutions describing newer achievements for the reactions of (arene)tricarbonyl-chromium and tricarbonyl(η5-cyclohexadienyl)manganese complexes (over 50 references).…”

1,4-Dinitro-1H-imidazoles

“…12 Over a dozen years ago, two reviews briefly reported on cine and ANRORC reactions of 1,4-dinitro-1H-imidazoles with nucleophiles. 13,14 Compound 1 is a versatile reagent that can be applied not only to the preparation of dinitroimidazole 8, as was mentioned earlier, but it is also a starting material for convenient syntheses of 5(4)-alkoxy-4(5)-nitro-1H-imidazoles (11), 5(4)-amino-4(5)-nitro-1H-imidazoles (12), and particularly of 1-alkyl-4-nitro-1H-imidazoles (13) and 1-aryl-4-nitro-1H-imidazoles (14) (Figure 3). Methyl derivatives 2 or 3 undergo similar transformations as dinitroimidazole 1.…”

“…48 The products served as starting materials in syntheses of adenines. Two other compounds, the (1)(2)(3)(4)(5)(6)(7)(8)(9)(10)(11)(12)(13)(14)(15) N)adenine and (1-3 H)ribose, were also prepared. The compounds were then enzymatically coupled to isotopically modified ribosyl groups to give respectively substituted adenosines (31, Figure 5).…”

“…N)imidazol-1′-yl]acetic acid was obtained. The latter acid with bromine and phosphorus trichloride in anhydrous benzene formed a product that was subjected to hydrolysis to afford 2-methyl-4(5)-nitro-1H- (1)(2)(3)(4)(5)(6)(7)(8)(9)(10)(11)(12)(13)(14)(15) N)imidazole in 40% yield. Starting compound 2 was also treated with ( 15 N)ammonia to produce a mixture of isotopically modified and natural nitrous oxide.…”

tele Nucleophilic Substitutions of Hydrogen in m‐(Trichloromethyl)nitrobenzenes with Cyano and Ester Carbanions

“…A general discussion and numerous examples of these processes are presented in a recent review by Suwiń ski and Ś wierczek. [5] Since the publication of this review, nine papers have reported tele substitution between nucleophiles and electron-deficient arenes. These arenes are 6-(1,2-dibromo-2-phenylethyl)pteridinediones, dichloropyrazines, N-fluoropyridinium fluoride, 2-(1-chloropropyl)imidazole hydrochlorides, 3-trichloromethyl-1,2,4-triazines, [(η 6 -arene)tricarbonyl]chromium or tricarbonyl(η 5 -cyclohexadienyl)manganese complexes, and halogenomethylnitrobenzenes.…”