title: Catalysis with Chalcogen Bonds.
abstract: Herein, we introduce catalysts that operate with chalcogen bonds. Compared to conventional hydrogen bonds, chalcogen bonds are similar in strength but more directional and hydrophobic, thus ideal for precision catalysis in apolar solvents. For the transfer hydrogenation of quinolines and imines, rate enhancements well beyond a factor of 1000 are obtained with chalcogen bonds. Better activities with deeper σ holes and wider bite angles, chloride inhibition and correlation with computed anion binding energies are consistent with operational chalcogen bonds. Comparable to classics, such as 2,2'-bipyrroles or 2,2'-bipyridines, dithieno[3,2-b;2',3'-d]thiophenes (DTTs), particularly their diimides, but also wide-angle cyclopentadithiazole-4-ones are identified as privileged motifs to stabilize transition states in the focal point of the σ holes on their two co-facial endocyclic sulfur atoms.
authors.affiliation: Department of Organic Chemistry, University of Geneva, Geneva, Switzerland.
authors.forename: Sebastian
authors.initials: S
authors.lastname: Benz
authors.affiliation: Department of Organic Chemistry, University of Geneva, Geneva, Switzerland.
authors.forename: Javier
authors.initials: J
authors.lastname: López-Andarias
authors.affiliation: Department of Organic Chemistry, University of Geneva, Geneva, Switzerland.
authors.forename: Jiri
authors.initials: J
authors.lastname: Mareda
authors.affiliation: Department of Organic Chemistry, University of Geneva, Geneva, Switzerland.
authors.forename: Naomi
authors.initials: N
authors.lastname: Sakai
authors.affiliation: Department of Organic Chemistry, University of Geneva, Geneva, Switzerland.
authors.forename: Stefan
authors.identifier: 0000-0002-8537-8349
authors.initials: S
authors.lastname: Matile
keywords: chalcogen bonds; dithienothiophenes; homogeneous catalysis; transfer hydrogenation