Utility of Ligand Effect in Homogenous Gold Catalysis: Enabling Regiodivergent π-Bond-Activated Cyclization

Abstract

Comprehensive utilization of both electronic and steric properties of ligands in homogeneous gold catalysis is achieved in the regiodivergent intramolecular hydroarylation of alkynes. A flexible electron-deficient phosphite ligand, combined with the readily transformable directing group methoxyl amide, is attached to a cationic Au(I) center in three-coordinate mode, affording sterically hindered ortho-position cyclization. Meanwhile, para-position cyclization is exclusively achieved with the assistance of a rigid electron-abundant phosphine ligand-based Au(I) catalyst, in which ligands manifest the compensating effect for cyclization through steric hindrance and electronic properties. By combining gold with silver catalysts, tetrahydropyrroloquinolinones possessing a congested tricyclic structure are obtained via a proven Au/Ag relay catalytic process.

Iron(III)‐Promoted Synthesis of 3‐(Organoselanyl)‐1,2‐Dihydroquinolines from Diorganyl Diselenides and N‐Arylpropargylamines by Sequential Carbon‐Carbon and Carbon‐Selenium Bond Formation

“…The study to determine the best solvent for this reaction indicated that the use of dioxane and acetonitrile gave a complex product mixture, with dimethyl sulfoxide and N,N-dimethylformamide the starting material was recovered, and dichloroethane offered 2 a in moderated yield. However, a significant increase in the reaction yield was obtained when nitromethane was used as solvent ( Table 1, entries [10][11][12][13][14][15].…”

Stability andtransInfluence in Fluorinated Gold(I) Coordination Compounds

“…The catalytic activity of gold adducts is strongly influenced by the electronic environment of the Au centers , , . The results of this investigation indicate that such catalytic activity could be modulated via the fluorination of the ligands.…”

“…The catalytic activity of gold adducts is strongly influenced by the electronic environment of the Au centers. [1,21,[30][31][32][33][34] The results of this investigation indicate that such catalytic activity could be modulated via the fluorination of the ligands. When the shielding of the phosphorus atom rises, the positive charge of the gold atom increases, and the compound becomes more susceptible to suffer nucleophilic attacks in the Au center.…”

Selectivity Switch in a Rhodium(II) Carbene Triggered Cyclopentannulation: Divergent Access to Three Polycyclic Indolines

“…Regio‐ and stereodivergent catalytic processes provide a promising possibility by generating each one of the possible regio‐ and stereoisomers from the same starting materials . Several effective strategies have been developed, including ligand or catalyst control,, additive control, or simply changing reaction conditions ,. Of these studies, most of them are able to produce two isomers with excellent selectivity, while successful examples on delivering three or more divergent isomers are very rare and challenging .…”