Gold-Catalyzed Stereoselective Synthesis of Di- or Trisubstituted Olefins Possessing a 1,4-Diene Framework via Intramolecular Allylation of Alkynes

Abstract

The cationic gold(I)-catalyzed reaction of 1-alkynyl-2-allylsilylbenzenes with water results in intramolecular allylation of the alkynes via 7-exo-dig cyclization to give 1,4-dienes in good yield with excellent stereoselectivities.

Key words

catalysis - 1,4-dienes - allylation - allylsilanes - gold

References and Notes

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9

Use of phenol as a nucleophile in place of water gave a complex mixture.

14

AgNTf₂, PtCl₂, (PPh₃)₂PtCl₂/2AgNTf₂, and Sc(OTf)₃ did not show any catalytic activities. Furthermore, background reaction mediated by Tf₂NH did not proceed, either.

18

For details, see Supporting Information.

19

Another interesting alternative mechanism for the formation of 2, as suggested by one referee, involves initial formation of 3-allyl-1-silaindenes and their subsequent hydrolysis. Indeed, we have observed the formation of 2 from isolated 3-allyl-1-silaindenes under our reaction conditions. However, we were unable to detect such intermediates when monitoring the reaction of 1 by ^¹H NMR spectroscopy (see Supporting Information for further details). Nevertheless, we would like to thank the referee for this suggestion.