Development of New Cascade Type Reactions Catalyzed by Metal Hydrides

本研究旨在开发新的催化反应，其中金属氢化物起关键作用。苯基醇与α，β-不饱和醛在氢化钌存在下反应得到α-羟甲基酮。α-羟甲基酮在含氟有机杂化溶剂F-626中发生反醛醇反应。通过连续的氢化钌催化反应和热反醛反应，实现了酮类化合物的一锅合成。RuHCl(CO)(PPh_3)_3有效催化了分子内Tishchenko反应。烯酮与二醛的反应通过连续的C-C键和CO键生成酮乳，产率高。硼酸在盐酸（CO）（PPh_3）_3存在下与醛类反应生成酮类。Ir催化脱羰反应生成内烯烃，KI的加入大大加速了脱羰反应。原位催化烯烃异构化形成的Ir-H基团。

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.