無 溶 媒 触 媒 反 応 を 基 軸 と す る環 境 調 和 型 有 機 合 成

Carbon dioxide（CO₂）is not only a greenhouse gas but also a renewable C1 source that is important for organic synthesis. On the other hand, minimizing organic solvent is also an important subject from the viewpoint of fossil fuel, energy, resource, cost, safety, and environment. Here we summarize our achievements in solvent-free catalysis. We developed a series of bifunctional metalloporphyrin catalysts for the synthesis of cyclic carbonates or polycarbonates from epoxides and CO₂. As a result of structural optimizations, Mg and Zn porphyrins having quaternary ammonium bromide groups were suitable for the synthesis of cyclic carbonates（TOF ＝12,000―46,000 h⁻¹, TON＝55,000―310,000）. In contrast, bifunctional Al porphyrins were highly active for the copolymerization of cyclohexene oxide and CO₂ to give polycarbonates. The solvent-free reaction with a catalyst loading of 0.0025 mol% under CO₂（2 MPa）was conducted at 120 ℃ for 1 h to give poly（cyclohexene carbonate）: TOF＝10,000 h⁻¹, polycarbonate selectivity ＞99%, PDI＝1.02, and M_n＝68,000. The reaction with a catalyst loading of 0.001 mol% for 24 h gave polymers with a M_n of 281,000, which corresponded to 2,000-mer. The high catalytic activities resulted from the cooperative action of the central metal ion and the quaternary ammonium salts. Chiral catalysts for the kinetic resolution of terminal or internal epoxides with CO₂ were also developed. In addition, a BINOL derivative（L）was designed to make dinuclear metal complexes （M₂L）; unexpectedly, heating a mixture of M and L furnished macrocyclic multinuclear metal dependent ^complexes N ^such -formylation ^{as Zn5L3}／N ⁱⁿ -methylation ^{high yields,} of ^which amines ^showed with CO ^catalytic₂ and hydrosilane. ^{activities for} On ^the the ^temperature other hand, ^- tetrabutylammonium acetate catalyzed the solvent-free N-formylation of amines with CO₂ and hydrosilane to give formamides including Weinreb formamide, Me （MeO）NCHO, which was successively converted into aldehydes by one-pot reactions with Grignard reagents. In addition, the intermolecular or intramolecular asymmetric benzoin reaction was catalyzed by a small amount of N-heterocyclic carbene（NHC）under solvent-free conditions, and the solvent-free intramolecular asymmetric Stetter reaction also proceeded efficiently. In some cases, even solid-to-solid conversions took place.