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Extended Dötz‐Like Cyclization Reactions Towards the Synthesis of Eight‐Membered Ring‐Containing Polycycles: Scope and Theoretical Studies
Author(s) -
Barluenga José,
FañanásMastral Martín,
Palomero M. Angel,
Aznar Fernando,
Valdés Carlos
Publication year - 2007
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200700413
Subject(s) - scope (computer science) , ring (chemistry) , chemistry , computer science , organic chemistry , programming language
The reaction between cyclobutene‐containing dienyl Fischer carbene complexes (FCCs) and alkynes has been studied from both an experimental and a theoretical point of view. We have found that the reaction follows different pathways depending on the nature of the terminal double bond of the carbene complex. Thus, eight‐membered carbocycles have been obtained from an extended Dötz‐like reaction of dienyl FCCs and indolyl‐ or benzofuryl‐substituted alkenyl FCCs. On the other hand, phenyl‐ and naphthyl‐substituted alkenyl FCCs follow a typical benzannulation pathway giving rise to cyclohexadienones. DFT calculations have allowed us to formulate detailed mechanistic proposals and to provide an explanation for the formation of either the benzannulation products or the eight‐membered carbocycles.