Palladium-Catalyzed IntramolecularArylation Reaction: Mechanism and Application for theSynthesis of Polyarenes

Abstract

P a l l a d i u m -C a t a l y z e d I n t r a m o l e c u l a r A r y l a t i o n R e a c t i o n Abstract: The intramolecular palladium-catalyzed reaction of aryl bromides and triflates with arenes has been used for the preparation of polyarenes. The synthesis of benz[e]acephenantrylenes, corannulenes, and C 60 H 30 , a 'crushed fullerene', by using this methodology are presented. Mechanistic studies on the arylation step point to an electrophilic substitution reaction pathway.

Organometallic alkane CH activation

“…A related cyclometalation was applied to complex organic synthesis by Sames and coworkers [68] who report catalytic arylation (Suzuki reaction) and alkenylation (Heck reaction) of alkyl segments of a synthetic intermediate with Pd(II). Cyclometalation [69], has also been incorporated into a number of other catalytic reactions of organic synthetic interest [25,26,70,71], and seems capable of considerable elaboration in future. For example, [Ir(cod)(PR 3 ) 2 ]BF 4 and related species are catalysts of choice for the tritiation of drug molecules with chelate assisted selectivity [72].…”

Palladacycles in catalysis – a critical survey

“…Palladacyclic intermediates play important role in cascade transformations leading to complex molecular architectures ( [3,4]), and proximally (ortho or peri) directed arylation reactions (cf. e.g.…”

Efficient Routes to Acenaphthylene‐Fused Polycyclic Arenes/Heteroarenes and Heterocyclic Fluoranthene Analogues

“…[5] Similarly, the isolation of C 60 fullerene and higher fullerenes has aroused renewed interest in the chemistry of bowl-shaped PAHs, and many efforts have in recent years been directed towards the synthesis of polynuclear hydrocarbons containing peri-fused five-and six-membered ring carbon fragments corresponding to portions of fullerene surfaces (buckybowls). [6] Indeno-annulated polycyclic aromatic hydrocarbons such as fluoranthene, benzo [j]fluoranthene and benzo[k]fluoranthene have received considerable attention due to their resemblance to partial structures of C 60 fullerene and its higher homologues, their unusual (photo)physical properties and the carcinogenic activity exhibited by some representative compounds. [2d,7] The heterocyclic analogues of polycyclic aromatic hydrocarbons are also potentially useful organic donors in molecular devices, [8] and heterocyclic compounds with fused aromatic subunits such as porphyrin chromophores may show profound changes in the electronic properties of the porphyrin macrocycles.…”