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  Synthesis of Phenanthrenes and Polycyclic Heteroarenes by Transition-Metal Catalyzed Cycloisomerization Reactions

Mamane, V., Hannen, P., & Fürstner, A. (2004). Synthesis of Phenanthrenes and Polycyclic Heteroarenes by Transition-Metal Catalyzed Cycloisomerization Reactions. Chemistry – A European Journal, 10(18), 4556-4575. doi:10.1002/chem.200400220.

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 Creators:
Mamane, Victor1, Author              
Hannen, Peter1, Author              
Fürstner, Alois1, Author              
Affiliations:
1Research Department Fürstner, Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_1445584              

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Free keywords: arenes; homogeneous catalysis; natural products; phenanthrenes; platinum
 Abstract: Readily available biphenyl derivatives containing an alkyne unit at one of their ortho-positions are converted into substituted phenanthrenes on exposure to catalytic amounts of either PtCl2, AuCl, AuCl3, GaCl3 or InCl3 in toluene. This 6-endo-dig cyclization likely proceeds through initial π-complexation of the alkyne unit followed by interception of the resulting η2-metal species by the adjacent arene ring. The reaction is inherently modular, allowing for substantial structural variations and for the incorporation of substituents at any site of the phenanthrene product. Moreover, it is readily extended to the heterocyclic series as exemplified by the preparation of benzoindoles, benzocarbazoles, naphthothiophenes, as well as bridgehead nitrogen heterocycles such as pyrrolo[1,2-a]quinolines. Depending on the chosen catalyst, biaryls bearing halo-alkyne units can either be converted into the corresponding 10-halo-phenanthrenes or into the isomeric 9-halo-phenanthrenes; in the latter case, the concomitant 1,2-halide shift is best explained by assuming a metal vinylidene species as the reactive intermediate. The scope of this novel method for the preparation of polycyclic arenes is illustrated by the total synthesis of a series of polyoxygenated phenanthrenes that are close relatives of the anticancer agent combretastatin A-4, as well as by the total synthesis of the aporphine alkaloid O-methyl-dehydroisopiline and its naturally occurring symmetrical dimer.

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Language(s): eng - English
 Dates: 2004-03-072004-07-292004-09-20
 Publication Status: Published in print
 Pages: 20
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: eDoc: 219607
DOI: 10.1002/chem.200400220
ISI: 000224146800020
 Degree: -

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Title: Chemistry – A European Journal
  Other : Chem. – Eur. J.
  Other : Chem. Eur. J.
Source Genre: Journal
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Publ. Info: Weinheim, Germany : VCH Verlagsgesellschaft
Pages: - Volume / Issue: 10 (18) Sequence Number: - Start / End Page: 4556 - 4575 Identifier: ISSN: 0947-6539
CoNE: https://pure.mpg.de/cone/journals/resource/954926979058