This paper describes the superacid-catalyzed chemistry of olefinic amines and related compounds. A variety of olefinic amines are found to react with benzene in CF(3)SO(3)H (triflic acid) to give addition products in good yields (75-99%), including the pharmaceutical agents fenpiprane and prozapine. A general mechanism is proposed that invokes the formation of reactive, dicationic electrophiles and the direct observation of a diprotonated species is reported from low-temperature NMR experiments. This chemistry is also used to conveniently prepare functionalized polystyrene beads having pendant amine groups.

Superacid-Catalyzed Reactions of Cinnamic Acids and the Role of Superelectrophiles. -The chemistry of cinnamic acids and related compounds in the presence of benzene and triflic acid is studied. Two competing reaction mechanisms are proposed which both involve the formation of dicationic intermediates. The cinnamic acid affords indanone derivatives when the aryl group is not deactivated by substituents and give chalcone-type products when the aryl group is deactivated by strong electro-withdrawing groups. -(RENDY, R.; ZHANG, Y.; MCELREA, A.; GOMEZ, A.; KLUMPP*, D. A.; J.

Dedicated to Professor Joan Bosch on the occasion of his 60th anniversary AbstractThe 4,5-dihydropyrrolo[1,2-a]quinoxaline system was prepared through two different reaction sequences. The first method is based on the intramolecular reductive amination of the corresponding nitrophenylpyrrole-carbaldehyde intermediate, whereas an alternative synthesis involves as key step, the intramolecular substitution of an aromatic fluoride by a secondary amine.

2005 C-C bond formation O 0282Reactive Dications: The Superacid-Catalyzed Reactions of Alkynes Bearing Adjacent N-Heterocycles or Amine Groups. -Various title compounds react with triflic acid to generate dicationic electrophiles that are capable of reacting with benzene to give inter-or intramolecular products in good yields. The novel dicationic intermediates are composed of vinyl cations with adjacent positive charge centers (pyridinium, ammonium, etc.). -(KLUMPP*, D. A.; RENDY, R.; ZHANG, Y.; MCELREA, A.; GOMEZ, A.; DANG, H.; J.

Dicationic Intermediates Involving Protonated Amides: Dual Modes of ReactivityIncluding the Acylation of Arenes. -The starting amides form dicationic intermediates in the presence of superacid TfOH. The protonated amide group is able to increase the reactivity of adjacent electrophilic moieties such as carboxonium group and, thus, allowing its attack on benzene (II). On the other hand, adjacent cationic groups such as ammonium and pyridinium enhance the electrophilic reactivity of the protonated amide unit and enable the use of amides for acylation of arenes. -(KLUMPP*, D. A.; RENDY, R.; ZHANG, Y.; GOMEZ, A.; MCELREA, A.; Org.