Hydrogen-bonding catalysis of sulfonium salts.

Although quaternary ammonium and phosphonium salts are known as important catalysts in phase-transfer catalysis, the catalytic ability of tertiary sulfonium salts has not yet been well demonstrated. Herein, we demonstrate the catalytic ability of trialkylsulfonium salts as hydrogen-bonding catalysts on the basis of the characteristic properties of the acidic α hydrogen atoms on alkylsulfonium salts.

Hydrogen-Bonding Catalysis of Tetraalkylammonium Salts in an Aza-Diels-Alder Reaction.

A piperidine-derived tetraalkylammonium salt with a non-coordinating counteranion worked as an effective hydrogen-bonding catalyst in an aza-Diels-Alder reaction of imines and a Danishefsky diene. The hydrogen-bonding interaction between the ammonium salt and an imine was observed as part of a (1) H NMR titration study.

A new generation of chiral phase-transfer catalysts.

Phase-transfer catalysis has long been recognized as a versatile method for organic synthesis. In particular, over more than the past three decades, asymmetric phase-transfer catalysis based on the use of structurally well-defined chiral catalysts has become a topic of great scientific interest. Although various effective chiral catalysts have already been reported and these catalysts were utilized for practical asymmetric transformations, further design and development of new chiral phase-transfer catalysts are still attractive research subjects in organic chemistry due to the high utility and practicability of phase-transfer-catalyzed reactions. This review focuses on the recent examples of newly designed effective chiral phase-transfer catalysts.

Tetraalkylammonium Salts as Hydrogen-Bonding Catalysts.

Although the hydrogen-bonding ability of the α hydrogen atoms on tetraalkylammonium salts is often discussed with respect to phase-transfer catalysts, catalysis that utilizes the hydrogen-bond-donor properties of tetraalkylammonium salts remains unknown. Herein, we demonstrate hydrogen-bonding catalysis with newly designed tetraalkylammonium salt catalysts in Mannich-type reactions. The structure and the hydrogen-bonding ability of the new ammonium salts were investigated by X-ray diffraction analysis and NMR titration studies.