Palladium-Catalyzed Intramolecular Arylation Reaction: Mechanism and Application for the Synthesis of Polyarenes

Antonio M. Echavarren; Berta Gómez-Lor; Juan J. González; Óscar de Frutos

doi:10.1055/s-2003-38382

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Synlett 2003(5): 0585-0597
DOI: 10.1055/s-2003-38382

ACCOUNT

Palladium-Catalyzed Intramolecular Arylation Reaction: Mechanism and Application for the Synthesis of Polyarenes

Antonio M. Echavarren*^a, Berta Gómez-Lor^b, Juan J. González^a, Óscar de Frutos^a
^a Departamento de Química Orgánica, Universidad Autónoma de Madrid, Cantoblanco, 28049, Madrid, Spain
Fax: +34(913)973966; e-Mail: anton.echavarren@uam.es;
^b Instituto de Ciencia de Materiales, CSIC, Cantoblanco, 28049, Madrid, Spain

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Publication History

Received 1 March 2002
Publication Date:
28 March 2003 (online)

Abstract
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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 C₆₀H₃₀, a ‘crushed fullerene’, by using this methodology are presented. Mechanistic studies on the arylation step point to an electrophilic substitution reaction pathway.

1 Introduction
2 An Approach to the Synthesis of Fullerene Fragments based on the Palladium-Catalyzed Arylation
3 Synthesis of Benz[e]acephenantrylenes and Related
Polyarenes by Palladium-Catalyzed Arylation
4 An Approach to the Synthesis of Dibenzocorannulene
5 Mechanistic Insights into the Palladium-Catalyzed
Arylation Reaction
5.1 The Role of Phosphine Ligands
5.2 Electrophilic Substitution or C-H Activation?
6 Palladium Catalyzed Arylation Synthesis of C ₃ _h Polyarenes from Truxenes
7 Summary and Outlook

Key words

palladium - arylation - polyarenes - corannulenes - fullerene

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35

The analogous reaction of (E,E)-1,4-diphenylbutadiene with acenaphtylene(28) in 1,2-dichlorobenzene at 180 °C afforded a 2:1 mixture of endo and exo cycloadducts in 40% yield. The assignment of the configuration of the major compound as the endo isomer was tentatively based on the ¹H NMR data.