Gold-Catalyzed Cycloisomerization of 1,6-Diyne Carbonates and Esters to 2,4a-Dihydro‑1H‑fluorenes

A synthetic method to prepare 2,4a-dihydro-1H-fluorenes efficiently from gold(I)-catalyzed 1,2-acyloxy migration/cyclopropenation/Nazarov cyclization of 1,6-diyne carbonates and esters is described. The suggested reaction pathway provides rare examples of [2,3]-sigmatropic rearrangement in this clas...

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Published inJournal of the American Chemical Society Vol. 135; no. 21; pp. 7926 - 7932
Main Authors Rao, Weidong, Koh, Ming Joo, Li, Dan, Hirao, Hajime, Chan, Philip Wai Hong
Format Journal Article
LanguageEnglish
Published WASHINGTON American Chemical Society 29.05.2013
Amer Chemical Soc
Subjects
Chemistry
Chemistry, Multidisciplinary
Physical Sciences
Science & Technology
DUAL-ACTIVATION
MOLECULAR CALCULATIONS
TANDEM
EFFECTIVE CORE POTENTIALS
PROPARGYLIC ACETATES
VERSATILE
GOLD(I)-CATALYZED CYCLOISOMERIZATION
COMPLEXES
CYCLOPROPANATION
CYCLOPROPENES
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Summary:A synthetic method to prepare 2,4a-dihydro-1H-fluorenes efficiently from gold(I)-catalyzed 1,2-acyloxy migration/cyclopropenation/Nazarov cyclization of 1,6-diyne carbonates and esters is described. The suggested reaction pathway provides rare examples of [2,3]-sigmatropic rearrangement in this class of compounds as well as the involvement of an in situ formed cyclopropene intermediate in gold catalysis. Experimental and ONIOM(QM:QM′) [our own n-layered integrated molecular orbital and molecular mechanics(quantum mechanics:quantum mechanics′)] computational studies based on the proposed Au carbenoid species provide insight into this unique selectivity.
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ISSN:0002-7863
1520-5126
DOI:10.1021/ja4032727