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[W(CO) 5 ]‐Catalyzed endo‐ or exo ‐Cycloisomerization Reactions of 1,1‐Disubstituted 4‐Pentyn‐1‐ols: Experimental and Theoretical Studies
Author(s) -
Barluenga José,
Diéguez Alejandro,
Rodríguez Félix,
Fañanás Francisco J.,
Sordo Tomás,
Campomanes Pablo
Publication year - 2005
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.200500537
Subject(s) - cycloisomerization , catalysis , chemistry , alkyl , substitution (logic) , medicinal chemistry , stereochemistry , computational chemistry , organic chemistry , philosophy , linguistics
The [W(CO) 5 ]‐catalyzed cycloisomerization reaction of 1,1‐disubstituted 4‐pentyn‐1‐ol derivatives has been studied from both, an experimental and theoretical point of view. Three different catalytic systems have been evaluated {preformed [(thf)W(CO) 5 ], [W(CO) 6 ]/excess Et 3 N, and [W(CO) 6 ]/2 mol % Et 3 N]. We have found that the reaction proceeds to give the formal endo ‐ or exo ‐cycloisomerization products depending on the amount of Et 3 N used and on the substitution along the alkyl chain of the starting alkynol. The theoretical study allowed us to find the mechanisms of the reactions which explain the formation of the formal endo ‐ or exo ‐cycloisomerization products.