Gold(I)-Catalyzed 1,6-Enyne Single-Cleavage Rearrangements: The Complete Picture

We identify the factors that rule the selectivity in single-cleavage skeletal rearrangements promoted by gold­(I) catalysts. We find that stereoconvergence is enabled by a rotational equilibrium when electron-rich substituents are used. The anomalous Z-selective skeletal rearrangement is found to be...

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Published inACS Organic & Inorganic Au Vol. 3; no. 5; pp. 312 - 320
Main Authors García-Padilla, Eduardo, Maseras, Feliu, Echavarren, Antonio M.
Format Journal Article
LanguageEnglish
Published American Chemical Society 04.10.2023
Subjects
gold carbenes
metal carbenes
DFT mechanistic study
enynes
cycloisomerization
rearrangements
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Summary:We identify the factors that rule the selectivity in single-cleavage skeletal rearrangements promoted by gold­(I) catalysts. We find that stereoconvergence is enabled by a rotational equilibrium when electron-rich substituents are used. The anomalous Z-selective skeletal rearrangement is found to be due to electronic factors, whereas endo-selectivity depends on both steric and electronic factors.
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ISSN:2694-247X
2694-247X
DOI:10.1021/acsorginorgau.3c00028