Cyclization, Ring-Expansion, and Several Cascade Reactions Utilizing Allenylic Molecular Structure Characteristics
Cyclization, Ring-Expansion, and Several Cascade Reactions Utilizing Allenylic Molecular Structure Characteristics
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利用烯键式分子结构特征进行环化、扩环和多个级联反应
DOI：
10.5059/yukigoseikyokaishi.61.1088
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发表时间：
2003
影响因子：
0.2
通讯作者：
S. Sano
中科院分区：
文献类型：
--
作者：
Y. Nagao;S. Sano
介绍了基于烯丙基分子结构特征的各种新反应。具体地说，α-乙酰氨基(或甲氧基)-α-炔基丙二酸二乙酯的温和碱性水解会生成共轭的烯丙基酯，从而促进5-内式杂环环化，得到三取代恶唑、SH-酶抑制、新的手性吡咯烷酮(组织蛋白酶B抑制剂)的形成，以及级联反应的Myers型双自由基芳构化。用许多共轭的烯丙基酮和Lewis酸完成了系统的邻位-邻位-内向-模式、双螺内向-内向和间安萨-内向-环化反应。用羟基取代的烯丙基环类化合物实现了碱催化和钯(0)催化的级联杂环和碳环扩环反应。
Various kinds of new reactions based on allenylic molecular structure characteristics have been described. Specifically, mild alkaline hydrolysis of diethyl α-acetylamino (or methoxy) -α-alkynylmalonates generates conjugated allenyl esters which promote 5-endo-mode heterocyclic cyclization giving trisubsutituted oxazoles, SH-enzyme inhibition, new chiral pyrrolinones (cathepsin B inhibitors) formation, and Myers-type biradical aromatization in a cascade reaction manner. Systematic ortho vicinal-endo-mode-, geminal spiro-endo-mode-, and meta ansa-endo-mode-cyclization reactions have been accomplished by using numerous conjugated allenyl ketones and Lewis acids. Base-mediated and palladium (0) -catalyzed cascade heterocyclic and carbocyclic ring-expansion reactions have been achieved by using hydroxy-substituted allenyl cyclic compounds.