Synthesis and chemical application s of ansa-type compounds

柄型化合物的合成及化学应用

• 批准号: 15590016
• 负责人: SATO Masayuki
• 金额: $ 2.3万
• 依托单位: University of Shizuoka
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2003
• 资助国家: 日本
• 起止时间: 2003 至 2004
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-15590016/
• 关键词: ansa compound; acylketene; pyridinophane; heterophane; crown ether; planar chiral compound; chiral carbene; intramolecular cycloaddition; ピリジノファン; 光学分割試薬; イミドイルケテン; ケテン; ヘテロファン合成; ワークベンチ; 4+2付加環化

Aromatic compounds bridged at the meta or para positions are referred to ansa compounds. This class of compounds is chemically and biologically useful. For example, ansamycin and its analogs are powerful antibiotics and pyridinophane-type crown ethers serve as excellent host for metals. However, these ansa-type compounds are not readily accessible due to their much strain by the strained bridged structure.We have studied a new method for synthesizing ansa-type compounds and their use in molecular recognition chemistry.Previously, we found that acylketenes can be generated most conveniently by thermal fragnentation of 1,3-dioxin-4-one derivatives. Based on this finding, we studied generation of bis(acylketene) and their intramolecular cyclization to produce ansa-type compounds. This project was very much successful. A series of 4-hydroxy-2-pyrones and 2-pyridines bridged at the 3- and 6-positions was synthesized by the intramolecular cyclization of bis(acylketene) intermediate highly effciently. These ansa-type compounds have planar chirality and served as excellent resolution reagent for chiral primary amines. Enantiomerically pure amines thus obtained were applied to the first synthesis of chiral imidazolium carbenes that proved to be useful catalyst for kinetic resolution of chiral alcohols. Pyridinophane-type 12-crown-4 was synthesized by ring transformation of the bridged 4-hydroxy-2-pyrones.We have also studied synthesis of bridged pyrones by metal-catalyzed ring-closing metathesis to that increasing attention has been diected toward the synthesis of medium and large rings inclucing cyclophanes. The results indicated that ring-closing metathesis afford the bridged pyrones in much lower yields than that by intramolecular cycloaddition of bis (acylketene).

在元位或PARA位置桥接的芳族化合物转介给ANSA化合物。这类化合物在化学和生物学上都是有用的。例如，Ansamycin及其类似物是强大的抗生素，吡啶二氨基型冠状醚是金属的绝佳宿主。但是，这些ANSA型化合物由于紧张的桥接结构的很大压力而无法轻易获得。我们研究了一种合成ANSA型化合物及其在分子识别化学中的新方法。通过1,3-二氧蛋白-4-衍生物的热脆性最方便地生成。基于这一发现，我们研究了BIS（酰基酮）及其分子内环化的产生，以产生ANSA型化合物。这个项目非常成功。由BIS（酰基酮烯）中间体的分子内环化合成了一系列的4-羟基-2-吡喃和2-吡啶，在3个位置上桥接了3个位置和6位。这些ANSA型化合物具有平面性手性，可作为手性原胺的出色分辨率试剂。因此，将其获得的对映体纯胺应用于手性咪唑甲苯的首次合成，这些胺被证明是手性醇的动力学分辨率有用的催化剂。吡啶酚型12克4通过桥接的4-羟基-2-碳的环转化合成。我们还研究了通过金属催化的环闭环节的合成桥接的pyrones的合成，使人们对越来越多的注意力降低了关注的趋势。中等和大环，包括环流。结果表明，与分子内环载物（酰基酮烯）相比，闭合环的旋转的桥梁的产量低得多。

项目成果

Chiral N-heterocyclic carbenes as asymmetric acylation catalysts

• DOI: 10.1016/j.tet.2005.09.071
• 发表时间: 2006-01
• 期刊: Tetrahedron
• 影响因子: 2.1
• 作者: Yumiko Suzuki;K. Muramatsu;K. Yamauchi;Yasuko Morie;Masayuki Sato

Efficient synthesis of pyridinophanes by intramolecular cycloaddition of Bis(acylketene)

双酰基乙烯酮分子内环加成高效合成吡啶芬

• 发表时间: 2006
• 作者: K.Suwa;K.Fusazaki;Y.Suzuki;K.Ikeda;M.Sato
• 通讯作者: M.Sato

佐藤雅之他: "A new method for synthesis of crown ether type pyridinophanes"Heterocycles. 60. 899-908 (2003)

Masayuki Sato 等：“冠醚型吡啶并芬的合成新方法”Heterocycles 60. 899-908 (2003)。

A new method for synthesis of crown ether type pyridinophanes

冠醚型吡啶并芬的合成新方法

• 发表时间: 2003
• 期刊: Heterocycles 60
• 作者: 佐藤雅之;他
• 通讯作者: 他

N-Heterocyclic carbenes as asymmetric acylation catalysts

N-杂环卡宾作为不对称酰化催化剂

• 发表时间: 2006
• 期刊: Tetrahedron 62
• 作者: 鈴木由美子;他
• 通讯作者: 他