Gold‐Catalyzed Homogeneous Oxidative Cross‐Coupling Reactions

Abstract

Oxidizing gold? A gold(I)/gold(III) catalytic cycle is essential for the first oxidative cross-coupling reaction in gold catalysis. By using Selectfluor for gold(I) oxidation, this chemistry reveals the synthetic potential of incorporating gold(I)/gold(III) catalytic cycles into contemporary gold chemistry and promises a new area of gold research by merging powerful gold catalysis and oxidative metal-catalyzed cross-coupling reactions.

Scope and Limitations of Palladium‐Catalyzed Cross‐Coupling Reactions with Organogold Compounds

“…Still, in the last years some examples have been reported, which include cross-couplings [3] and homocouplings, [4] homocoupling using external stoichiometric oxidants [5] like BAIB, [5a] t-BuOOH, [5b] or Selectfluor [5c] and cross-coupling using stoichiometric Selectfluor. [6] For a long time, alkenylgold species have been proposed as intermediates of gold-catalyzed reactions with allenes or alkynes. [7] These alkenylgold species usually regenerate the active catalyst by a fast protodeauration step, more seldom by trapping with alternative electrophiles.…”

Total synthesis of (+)-lentiginosine via a key Au catalysis

“…We have recently reported a formal [4+2] approach for the synthesis of piperidin-4-ones [13] via a key gold catalysis [14][15][16][17][18][19][20][21][22][23]. In this two-step sequence (Scheme 1), a secondary amine is initially alkylated with but-3-ynyl tosy late in a S N 2 reaction; subsequent m-CPBA oxidation of the formed tertiary amine into the corresponding N-oxide is followed by Au(I)-catalyzed intramolecular oxidation of the alkyne moiety, yielding an -oxo gold carbene intermediate (i.e., A); a formal carbene insertion into the CH bond  to the nitrogen atom presumably via sequential hydride migration and cyclization leads to an overall 4+2 annulation between a secondary amine (a C1 + N1 unit) and a but-3-ynyl moiety (a C4 unit).…”

Library-friendly synthesis of fluorinated ketones through functionalized hydration of alkynes and investigation of the reaction mechanism

“…The transmetalation of Au(I)-Cl complex with boronic acid has been demonstrated by Hashmi and co-workers in a recent paper [28]. The transmetalation of Au-F with boronic acid has also been proposed by Zhang and co-workers in their gold catalyzed crosscoupling reaction of propargylic acetate [29]. We believe that the strong B-F bond and the weak Au-F bond are the driving forces behind this transmetalation.…”