Gold-catalyzed propargylic substitutions: Scope and synthetic developments

• Olivier Debleds,
• Eric Gayon,
• Emmanuel Vrancken and
• Jean-Marc Campagne

Beilstein J. Org. Chem. 2011, 7, 866–877, doi:10.3762/bjoc.7.99

• substitutions on propargylic (allylic, benzylic) alcohols, with various nucleophiles (and bi-nucleophiles) based on the σ- and/or π-acidity of gold(III) complexes. Synthetic developments are also briefly described. Keywords: direct substitutions; gold; isoxazolines; propargylic substitutions; Introduction In

• allenic positions [6], and iii) compared to allylic and benzylic substitutions these reactions have been studied to a far lesser extent. Direct propargylic substitutions have traditionally and efficiently been carried out using the Nicholas [7] conditions but this implies the use of stoichiometric amounts

• ruthenium catalysts for asymmetric propargylic substitutions were next developed using acetone, hydrides and electron rich aromatics as nucleophiles [16][17][18]. In 2003, oxo-rhenium catalysts were introduced by Toste [19][20][21]. Substitution products were obtained in high yields with alcohols