I. Rhodium-Catalysed Carbometalation of Ynamides using Organoboron Reagents. As an expansion of existing procedures for the carbometalation of ynamides, it was discovered that [Rh(cod)(MeCN)2]BF4 successfully promotes the carbometalation of ynamides with organoboron reagents. A variety of organoboron reagents were found to be suitable for this reaction, but mostly the use of arylboronic acids was explored. The developed methodology provides β,β-disubstituted enamide products in a regio- and stereocontrolled manner. II. Palladium-Catalysed Hydroacyloxylation of Ynamides. In the presence of palladium(II) acetate, ynamides successfully underwent a hydroacyloxylation reaction with a variety of carboxylic acids. This carboxylic acid addition occurred highly regio- and stereoselectively to provide α-acyloxyenamides. Applications of the α-acyloxyenamide products were also investigated. III. Rhodium-Catalysed [2+2] Cycloaddition of Ynamides with Nitroalkenes. A novel rhodium catalyst system has been developed in order to promote the [2+2] cycloaddition reaction between ynamides and nitroalkenes. The reaction provides cyclobutenamide products and was diastereoselective in favour of the trans cyclobutenamide. Both the ynamide scope and the nitroalkene scope of the reaction have been explored.

京都大学 / 新制・論文博士 / 博士(工学) / 乙第13456号 / 論工博第4196号 / 新制||工||1770(附属図書館) / (主査)教授 中村 正治, 教授 大江 浩一, 教授 村田 靖次郎 / 学位規則第4条第2項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM