Mechanism of Photoredox-Initiated C–C and C–N Bond Formation by Arylation of IPrAu(I)–CF₃ and IPrAu(I)–Succinimide

Herein, we report on the photoredox-initiated gold-mediated C­(sp2)–CF3 and C­(sp2)–N coupling reactions. By adopting gold as a platform for probing metallaphotoredox catalysis, we demonstrate that cationic gold­(III) complexes are the key intermediates of the C–C and C–N coupling reactions. The high-valent gold­(III) intermediates are accessed by virtue of photoredox catalysis through a radical chain process. In addition, the bond-forming step of the coupling reactions is the reductive elimination from cationic gold­(III) intermediates, which is supported by isolation and crystallographic characterization of key Au­(III) intermediates

Mechanism of Photoredox-Initiated C–C and C–N Bond Formation by Arylation of IPrAu(I)–CF₃ and IPrAu(I)–Succinimide

Herein, we report on the photoredox-initiated gold-mediated C­(sp2)–CF3 and C­(sp2)–N coupling reactions. By adopting gold as a platform for probing metallaphotoredox catalysis, we demonstrate that cationic gold­(III) complexes are the key intermediates of the C–C and C–N coupling reactions. The high-valent gold­(III) intermediates are accessed by virtue of photoredox catalysis through a radical chain process. In addition, the bond-forming step of the coupling reactions is the reductive elimination from cationic gold­(III) intermediates, which is supported by isolation and crystallographic characterization of key Au­(III) intermediates

Synthesis of Indenyl Ethers by Gold(I)-Catalyzed Intramolecular Carboalkoxylation of Alkynes

The gold(I)-catalyzed carboalkoxylation of alkynes to form indanone derivatives from readily available ortho-acetylenic benzylic ethers is described. Importantly, the gold(I)-catalyzed rearrangement of enantioenriched benzylic ethers proceeds with chirality transfer, thus providing a practical method for the enantioselective synthesis of indenyl ethers

Gold(I)-Catalyzed Enantioselective Ring Expansion of Allenylcyclopropanols

Gold(I)-Catalyzed Enantioselective Ring Expansion of Allenylcyclopropanol

Gold(I)-Catalyzed Enantioselective Ring Expansion of Allenylcyclopropanols

Gold(I)-Catalyzed Enantioselective Ring Expansion of Allenylcyclopropanol

Direct Asymmetric Amination of α‑Branched Cyclic Ketones Catalyzed by a Chiral Phosphoric Acid

Here we report the direct asymmetric amination of α-substituted cyclic ketones catalyzed by a chiral phosphoric acid, yielding products with a N-containing quaternary stereocenter in high yields and excellent enantio­selectivities. Kinetic resolution of the starting ketone was also found to occur on some of the substrates under milder conditions, providing enantio­enriched α-branched ketones, another important building block in organic synthesis. The utility of this methodology was demonstrated in the short synthesis of (<i>S</i>)-ketamine, the more active enantiomer of this versatile pharmaceutical

Direct Asymmetric Amination of α‑Branched Cyclic Ketones Catalyzed by a Chiral Phosphoric Acid

Here we report the direct asymmetric amination of α-substituted cyclic ketones catalyzed by a chiral phosphoric acid, yielding products with a N-containing quaternary stereocenter in high yields and excellent enantio­selectivities. Kinetic resolution of the starting ketone was also found to occur on some of the substrates under milder conditions, providing enantio­enriched α-branched ketones, another important building block in organic synthesis. The utility of this methodology was demonstrated in the short synthesis of (<i>S</i>)-ketamine, the more active enantiomer of this versatile pharmaceutical

Gold(I)-Catalyzed Enantioselective Carboalkoxylation of Alkynes

A highly enantioselective carboalkoxylation of alkynes catalyzed by cationic (DTBM-MeO-Biphep)­gold­(I) complexes is reported. Various optically active β-alkoxyindanone derivatives were obtained in good yields with high enantioselectivities. Furthermore, this methodology was extended to the enantioselective synthesis of 3-methoxycyclopentenones. The reaction is proposed to proceed through an enantioselective cyclization of intermediates containing vinylgold­(I) and prochiral oxocarbenium moieties

Enantioselective Total Synthesis of (−)-Galanthamine

Enantioselective Total Synthesis of (−)-Galanthamin

Asymmetric O- and C-Alkylation of Phenols

Asymmetric O- and C-Alkylation of Phenol