Recent Developments in Asymmetric Phase‐Transfer Reactions

Phase‐transfer catalysis has been recognized as a powerful method for establishing practical protocols for organic synthesis, because it offers several advantages, such as operational simplicity, mild reaction conditions, suitability for large‐scale synthesis, and the environmentally benign nature of the reaction system. Since the pioneering studies on highly enantioselective alkylations promoted by chiral phase‐transfer catalysts, this research field has served as an attractive area for the pursuit of “green” sustainable chemistry. A wide variety of asymmetric transformations catalyzed by chiral onium salts and crown ethers have been developed for the synthesis of valuable organic compounds in the past several decades, especially in recent years.     

Quinones synthesis via hydrogen peroxide oxidation of dihydroxy arenes catalyzed by homogeneous and macroporous-polymer-supported ruthenium catalysts

Ruthenium(II)/dimethyl phenyloxazoline (Ru(II)/dm-Pheox) complex 2a and its macroporous-polymeric-catalyst 4 were found to be very rapid and efficient catalysts in the hydrogen peroxide oxidation of 1,2- and 1,4-dihydroxy arenes. Most of the quinone products were delivered in 99% yield. The polymeric-catalyst 4 could be reused at least five times.     

Conductive liquid crystalline compounds having a piperazine structure

New conductive thermotropic liquid crystalline materials having a piperazine ring in the central core: 1-[4-(9-decenyloxy)phenyl]-4-alkylpiperazines (6) were synthesized. The mesomorphic behaviours of these compounds and their conductivity in the liquid crystal phase were measured. The principal features of these compounds are to exhibit a smectic B phase around room temperature (for example 6: Cr 50 SmB 81 I, °C) and to exhibit a large dark current (6d: 430 μA cm^?2, applied voltage 20 V, at 70°C) in the smectic B phase.     

Asymmetric phase-transfer reactions under base-free neutral conditions

Although quaternary onium salt-catalyzed phase-transfer reactions are generally believed to require base additives, we discovered even without any base additives conjugate additions of 3-substituted oxindoles proceeded smoothly in the presence of lipophilic quaternary onium bromide under water-organic biphasic conditions. The mechanism of this novel base-free neutral phase-transfer reaction system was investigated, and the assumed catalytic cycle was presented together with interesting effects of water and lipophilicity of the phase-transfer catalyst. The base-free neutral phase-transfer reaction system could be applied to highly enantioselective conjugate additions, aldol reaction, sulfenylation, and chlorination under the influence of chiral bifunctional onium bromides as key catalysts.     

Site‐Selective CH Borylation of Quinolines at the C8 Position Catalyzed by a Silica‐Supported Phosphane–Iridium System

Site‐selective C? H borylation of quinoline derivatives at the C8 position has been achieved by using a heterogeneous Ir catalyst system based on a silica‐supported cage‐type monophosphane ligand SMAP. The efficient synthesis of a corticotropin‐releasing factor₁ (CRF₁) receptor antagonist based on a late‐stage C? H borylation strategy demonstrates the utility of the C8 borylation reaction.     

A Base‐Free Neutral Phase‐Transfer Reaction System

Although phase‐transfer reactions catalyzed by using quaternary ammonium salts are generally believed to require base additives, we discovered that, even without any base additives, conjugate additions of 3‐substituted oxindoles to nitroolefins proceeded smoothly in the presence of lipophilic quaternary ammonium bromide under water–organic biphasic conditions. The mechanism of this novel base‐free neutral phase‐transfer reaction system is investigated and the assumed catalytic cycle is presented together with interesting effects of water and lipophilicity of the phase‐transfer catalyst. The base‐free neutral phase‐transfer reaction system can be applied to highly enantioselective conjugate addition and aldol reactions under the influence of chiral bifunctional ammonium bromides as key catalysts. The structure of the chiral ammonium enolate intermediate is discussed based on the single‐crystal X‐ray structures of relevant ammonium salts and the importance of bifunctional design of catalyst is clearly explained in the model of intermediate.     

Electrochemical Synthesis of Thienoacene Derivatives: Transition-Metal-Free Dehydrogenative C−S Coupling Promoted by a Halogen Mediator

The first electrochemical dehydrogenative C−S bond formation leading to thienoacene derivatives is described. Several thienoacene derivatives were synthesized by dehydrogenative C−H/S−H coupling. The addition of ⁿBu₄NBr, which catalytically promoted the reaction as a halogen mediator, was essential.