Gold‐Catalyzed Cycloisomerizations of Functionalyzed Cyclopropyl Alkynes: the Cases of Carboxamides and Alcohols

Push‐pull alkynylcyclopropane derivatives are claimed as suitable and active substrates for gold‐catalyzed transformations. Thus, 2(3H)‐azepinones can be readily prepared from alkynylcyclopropanecarboxamides through a nucleophilic addition/cyclopropane ring‐opening cascade process and, in this manus...

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Bibliographic Details
Published in:Advanced synthesis & catalysis 2017-09, Vol.359 (17), p.3035-3051
Main Authors: Fernández‐García, Jesús M., Garro, Hugo A., Fernández‐García, Laura, García‐García, Patricia, Fernández‐Rodríguez, Manuel A., Merino, Isabel, Aguilar, Enrique
Format: Article
Language:English
Subjects:
Adducts
Alcohols
Alkynes
Cascade chemical reactions
Cyclopropane
Gold
Heptanes
Isomerization
nucleophilic addition
Organic compounds
pyranones
ring expansion
Ring opening
seven-membered heterocycles
Substrates
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Summary:Push‐pull alkynylcyclopropane derivatives are claimed as suitable and active substrates for gold‐catalyzed transformations. Thus, 2(3H)‐azepinones can be readily prepared from alkynylcyclopropanecarboxamides through a nucleophilic addition/cyclopropane ring‐opening cascade process and, in this manuscript, the scope and the limitations of such reaction sequence are reported. The cascade reaction is general and occurs with complete regio‐ and quimioselection to form the seven‐membered heterocycles with the exception of primary alkyl‐substituted alkynylcyclopropanecarboxamides that render 4‐methoxy‐6‐oxo‐4‐enenitriles in moderate yields. Additionally, less activated alkynylcyclopropylmethanols undergo regioselective cycloisomerization at low temperature leading to oxabicyclo[4.1.0]heptanes. Notably, the cyclopropane ring opening of these adducts takes place under thermal conditions to form dihydropyranones.
ISSN:1615-4150
1615-4169
DOI:10.1002/adsc.201700264