Development of New Cascade Type Reactions Catalyzed by Metal Hydrides

本研究旨在开发新的催化反应，其中金属氢化物物种发挥关键作用。苄醇与α，β-不饱和醛在氢化物存在下反应生成α-羟甲基酮。α-羟甲基酮在氟-有机混合溶剂F-626中发生逆羟醛缩合反应。通过钌的催化反应和热逆羟醛缩合反应实现了酮的一锅合成。RuHCl（CO）（PPh_3）_3能有效地催化分子内Tishchenko反应。烯酮与二醛反应，通过连续的C-C键和CO键的形成，以良好的产率得到酮内酯。硼酸与醛在RuHCl（CO）（PPh_3）_3存在下反应生成酮。发生铱催化脱羰反应得到内烯烃，其中加入KI显着加速脱羰反应。原位生成的Ir-H物种催化烯烃异构化。

This research aimed at development of new catalytic reactions in which metal hydride species play a key role. The reaction of benzylic alcohols with α,β-unsaturated aldehydes in the presence of ruthenium-hydride gave α-hydroxymethyl ketones. α-Hydroxymethyl ketones underwent retro-aldol reaction in fluorous-organic hybrid solvent, F-626. One-pot procedure for the synthesis of ketones has also been achieved by the consecutive ruthenium hydride-catalyzed reaction and the thermal retro-aldol reaction. RuHCl(CO)(PPh_3)_3 effectivly catalyzed intramolecular Tishchenko reaction. The reaction of enones with dialdehydes gave keto lactons in good yields via sequential C-C and CO bond formation. Boronic acids react with aldehydes in the presence of RuHCl(CO)(PPh_3)_3 to give ketones. Ir catalyzed decarbonylation took place to give internal olefins, where addition of KI dramatically accelerated the decarbonylation reactions. Ir-H species formed in situ catalyzed isomerization of olefins.