Experimental and Theoretical Study of the Effectiveness and Stability of Gold(I) Catalysts Used in the Synthesis of Cyclic Acetals

  1. Cordón, J. 1
  2. López-De-Luzuriaga, J.M. 1
  3. Monge, M. 1
  1. 1 Universidad de La Rioja
    info

    Universidad de La Rioja

    Logroño, España

    GRID grid.119021.a

Journal:
Organometallics

ISSN: 0276-7333

Year of publication: 2016

Volume: 35

Issue: 5

Pages: 732-740

Type: Article

Export: RIS
DOI: 10.1021/acs.organomet.5b01015 SCOPUS: 2-s2.0-84969812998 WoS: 000372210300016 GOOGLE SCHOLAR

Metrics

Cited by

  • Scopus Cited by: 7 (14-07-2021)

Journal Citation Reports

  • Year 2016
  • Journal Impact Factor: 3.862
  • Best Quartile: Q1
  • Area: CHEMISTRY, INORGANIC & NUCLEAR Quartile: Q1 Rank in area: 8/46 (Ranking edition: SCIE)
  • Area: CHEMISTRY, ORGANIC Quartile: Q1 Rank in area: 12/59 (Ranking edition: SCIE)

SCImago Journal Rank

  • Year 2016
  • SJR Journal Impact: 1.723
  • Best Quartile: Q1
  • Area: Inorganic Chemistry Quartile: Q1 Rank in area: 6/72
  • Area: Organic Chemistry Quartile: Q1 Rank in area: 17/189
  • Area: Physical and Theoretical Chemistry Quartile: Q1 Rank in area: 18/165

CiteScore

  • Year 2016
  • CiteScore of the Journal : 7.8
  • Area: Inorganic Chemistry Percentile: 93
  • Area: Organic Chemistry Percentile: 91
  • Area: Physical and Theoretical Chemistry Percentile: 87

Abstract

Different [AuL](+) fragments (L = tertiary phosphines, ylides, or NHC carbene) have been tested under mild conditions as suitable catalysts for the transformation of terminal or internal alkynes into the corresponding cyclic acetals upon reaction with ethylene glycol. We have obtained a moderate to negligible activity when using tertiary phosphines or nonstabilized ylides as ligands. However, a very high catalytic activity is reached when the IPr N-heterocyclic carbene ligand is used. We have analyzed the key stages in this type of gold-catalyzed reaction, namely, (i) electronic activation (alkynophilicity); (ii) protodeauration; and (iii) decomposition of the gold catalyst. The first two stages have been analyzed through DFT computation of the minimum-energy reaction pathways employing different catalysts. An explanation of the catalysts' stability has been proposed through the analysis of in situ time-resolved nuclear magnetic resonance spectra of the catalysts.