Gold-catalyzed cycloisomerization of 1,6-diyne carbonates and esters to 2,4a-dihydro-1 H-fluorenes

Research output: Journal Publications and Reviews (RGC: 21, 22, 62)21_Publication in refereed journalpeer-review

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Author(s)

  • Weidong Rao
  • Ming Joo Koh
  • Dan Li
  • Hajime Hirao
  • Philip Wai Hong Chan

Detail(s)

Original languageEnglish
Pages (from-to)7926-7932
Journal / PublicationJournal of the American Chemical Society
Volume135
Issue number21
Publication statusPublished - 29 May 2013
Externally publishedYes

Abstract

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. © 2013 American Chemical Society.

Citation Format(s)

Gold-catalyzed cycloisomerization of 1,6-diyne carbonates and esters to 2,4a-dihydro-1 H-fluorenes. / Rao, Weidong; Koh, Ming Joo; Li, Dan et al.

In: Journal of the American Chemical Society, Vol. 135, No. 21, 29.05.2013, p. 7926-7932.

Research output: Journal Publications and Reviews (RGC: 21, 22, 62)21_Publication in refereed journalpeer-review