Studies toward the total synthesis of marine natural products having an azaspiro ring system

具有氮杂螺环系统的海洋天然产物的全合成研究

• 批准号: 20590001
• 负责人: NAKAMURA Seiichi
• 金额: $ 3万
• 依托单位: Hokkaido University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2008
• 资助国家: 日本
• 起止时间: 2008 至 2010
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-20590001/
• 关键词: スピロリド類; ムスカリン受容体阻害作用; [6,5,5]-ジスピロケタール; 分子内ヘテロMichael反応; ヘミケタールアルコキシド; 立体エネルギー; 渡環型反応; Diels-Alder反応; テザー; 閉環メタセシス; [6.5,5]-ジスピロケタール; α-メチレンラクトン; 分子内へテロMlchael反応; [6, 5, 5]-ジスピロケタール; C10-C24フラグメント; MacroModel

Toward the total synthesis of spirolides, marine natural products with an azaspirocyclic system, the construction of E and BCD ring systems of these molecules have been explored. Diels-Alder reaction of the diene, prepared from L-glutamic acid, with a 7-membered α-methylene lactone exhibited complete regioselectivity and modest exo and diastereoface selectivity to provide the desired exo cycloadduct as the major product. Since all attempts to obtain the desired dispiroketal isomer from an acyclic precursor by tandem double hemiketal formation/hetero-Michael addition sequence met with failure, we turned our attention to the transannular reaction, and designed and synthesized a macrocyclic substrate.

本论文对含氮杂螺环的海洋天然产物螺内酯类化合物的全合成进行了研究，探索了该类化合物的E环和BCD环体系的构建。由L-谷氨酸制备的二烯与7元α-亚甲基内酯的Diels-Alder反应显示出完全的区域选择性和适度的外消旋和非对映异构体选择性，以提供所需的外消旋环加合物作为主要产物。由于所有试图从无环前体通过串联双半缩酮形成/杂迈克尔加成序列获得所需的双螺缩酮异构体的尝试都失败了，我们将注意力转向了跨环反应，并设计和合成了大环底物。

项目成果

Stereocontrolled Construction of 1, 2-cis-α-Glycosidic Linkages Using Glycosyl Diphenyl Phosphates and Synthesis of α-Galactosylceramide KRN7000

使用磷酸糖基二苯酯立体控制构建 1, 2-顺式-α-糖苷键并合成 α-半乳糖神经酰胺 KRN7000

• 发表时间: 2010
• 期刊: Trends Glycosci. Glycotechnol 22
• 作者: Nambu;H.; Nakamura;S.; Suzuki;N.; Hashimoto;S.
• 通讯作者: S.

Total synthesis of (+)-condylocarpine, (+)-isocondylocarpine, and (+)-tubotaiwine.

• DOI: 10.1021/ol102709s
• 发表时间: 2011-01-07
• 期刊: ORGANIC LETTERS
• 影响因子: 5.2
• 作者: Martin, Connor L.;Nakamura, Seiichi;Otte, Ralf;Overman, Larry E.
• 通讯作者: Overman, Larry E.

Asymmetric synthesis of neolignans (-)-epi-conocarpan and (+)-conocarpan via Rh(II)-catalyzed C-H insertion process and revision of the absolute configuration of (-)-epi-conocarpan.

• DOI: 10.1021/jo900502d
• 发表时间: 2009-06-05
• 期刊: The Journal of organic chemistry
• 作者: Natori Y;Tsutsui H;Sato N;Nakamura S;Nambu H;Shiro M;Hashimoto S
• 通讯作者: Hashimoto S

Stereoselective synthesis of a C1–C6 fragment of pinnatoxin A via a 1,4-addition/alkylation sequence

• DOI: 10.1016/j.tetasy.2008.04.013
• 发表时间: 2008-05
• 期刊: Tetrahedron-asymmetry
• 作者: Seiichi Nakamura;F. Kikuchi;S. Hashimoto*

海産毒スピロリドDの合成研究

海洋毒物螺环内酯D的合成研究

• 发表时间: 2011
• 作者: 戸井田明憲;猪狩俊博;讃井しおり;橋本俊一;中村精一
• 通讯作者: 中村精一