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Back Cover: Gold‐Catalyzed Cycloisomerization of 1,6,8‐Dienyne Carbonates and Esters to cis ‐Cyclohepta‐4,8‐diene‐Fused Pyrrolidines (Chem. Eur. J. 41/2014)
Author(s) -
Rao Weidong,
Berry Stuart Neil,
Chan Philip Wai Hong
Publication year - 2014
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.201490173
Subject(s) - cycloisomerization , moiety , alkyne , chemistry , diene , reactivity (psychology) , catalysis , stereochemistry , medicinal chemistry , selectivity , organic chemistry , medicine , natural rubber , alternative medicine , pathology
Remote control? Dictating the mode of reactivity of propargylic carbonates or esters afar from the CC bond! Whether propargylic carbonates and esters favor an initial 1,2‐ or 1,3‐acyloxy migration step, which can determine product selectivity, has been often shown to be influenced by substitution patterns and electronic variations on and near the alkyne moiety. In their Full Paper on page 13174 ff., P. W. H. Chan et al. show that the substitution pattern and electronic variation on the 1,3‐diene unit and not the alkyne moiety in Au I ‐catalyzed cycloisomerizations of 1,6,8‐dienyne carbonates and esters orchestrates the initial sigmatropic rearrangement step. The cascade process provided a convenient and expedient one‐step synthetic route to cis ‐cyclohepta‐4,8‐diene‐fused pyrrolidines in good to excellent yields at catalyst loadings as low as 2 mol %.