Okamoto Noriko
Faculty of Pharmaceutical Sciences, Hiroshima International University, 5-1-1 Hirokoshingai, Kure, Hiroshima 737-0112, Japan.
Yakugaku Zasshi. 2013;133(8):879-87. doi: 10.1248/yakushi.13-00152.
Tandem reactions for efficient construction of nitrogen-containing heterocycles were developed. One-pot platinum(II)-catalyzed synthesis of indoles and isoquinolines has been achieved via isocyanates, which were derived from a Hofmann-type rearrangement of 2-alkynylbenzamides and 2-alkynylbenzylamides using a hypervalent iodine reagent. As an extension of this approach, trans-2,3-dihydro-4-quinolones were synthesized via acid-catalyzed intermolecular [2+2]-cycloaddition of aldehydes and carbamates, which were formed from nucleophilic addition of alcohols to isocyanate intermediates. Direct, efficient syntheses of the benzimidazo[2,1-a]isoquinoline ring system have been achieved with 2-bromoarylaldehydes, terminal alkynes, and 1,2-phenylenediamines by a microwave-accelerated tandem process in which a Sonogashira coupling, 5-endo cyclization, oxidative aromatization, and 6-endo cyclization can be performed in a single synthetic operation.
开发了用于高效构建含氮杂环的串联反应。通过异氰酸酯实现了一锅法铂（II）催化的吲哚和异喹啉的合成，这些异氰酸酯是使用高价碘试剂由2-炔基苯甲酰胺和2-炔基苄基酰胺的霍夫曼型重排得到的。作为该方法的扩展，通过醛和氨基甲酸酯的酸催化分子间[2+2]环加成反应合成了反式-2,3-二氢-4-喹诺酮，醛和氨基甲酸酯是由醇对异氰酸酯中间体的亲核加成形成的。通过微波加速串联过程，使用2-溴芳基醛、末端炔烃和1,2-苯二胺实现了苯并咪唑并[2,1-a]异喹啉环系的直接高效合成，其中在单一合成操作中可以进行Sonogashira偶联、5-内型环化、氧化芳构化和6-内型环化。
