Organic Synthesis Using Oxiranyl Anions

使用环氧乙烷基阴离子的有机合成

• 批准号: 09672175
• 负责人: MORI Yuji
• 金额: $ 2.05万
• 依托单位: MEIJO UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 1997
• 资助国家: 日本
• 起止时间: 1997 至 1999
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-09672175/
• 关键词: oxiranyl anion; 6-endo cyclization; oxepane; polytetrahydropyran; epoxy sulfone; hemibrevetoxin B; marin polycyclic ether; アルキル化; 5-エンド閉環反応; テトラヒドロフラン; brown alga; (6S, 7S, 9R, 10R)-6, 9-epoxynonadec-18-ene-7, 10-diol; Notheia anoma; テトラヒドロピラ

Oxiranyl anions are nucleophilic and their reaction with a variety of electrophiles provides a new methodology for introducing an oxiranyl group directly into organic molecules. The generation and reaction of oxiranyl anions and their applications to natural product synthesis were carried out in this project.1. Alkylation of oxiranyl anionsSulfonyl-stabilized oxiranyl anions, gerenated by deprotonation of the corresponding epoxy sulfones with n-BuLi in THF at -100℃, reacted with trifluoromethanesulfonate esters (triflate) to give the coupled products in high yield.2. Synthesis of polytetrahydropyrans by 6-endo cyclizationThe new method for the synthesis of trans-fused polytetrahydropyrans was developed. The approach involves two key reactions : (i) alkylation of a sulfonyl-stabilized oxiranyl anion with a triflate, (ii) acid-promoted 6-endo cyclization of the resulting hydroxy epoxy sulfone assisted by the electron-withdrawing sulfonyl group.3. Synthesis of methyl-substituted 6 membered cyclic ethers.A general procedure for the synthesis of tetrahydropyrans having methyl groups adjacent to the ring oxygen was developed based on the 6-endo cyclization of methyl-substituted hydroxy epoxy sulfones.4. Synthesis of Hemibrevetoxin BHemibrevetoxin B is one of polycyclic ether marine toxins isolated from the cultured cells of the red tide organism Gymnodinium breve and has the unique 6,6,7,7-tetracyclic ether ring system. The formal total synthesis of hemibrevetoxin B was accomplished by using oxiranyl anion strategy.

环氧乙烷基阴离子是亲核的，它们与各种亲电试剂的反应提供了一种将环氧乙烷基直接引入有机分子的新方法。本项目主要研究环氧乙烷基阴离子的生成、反应及其在天然产物合成中的应用.环氧乙烷基阴离子的烷基化反应在-100℃下，用正丁基锂（n-BuLi）使相应的环氧砜去质子化，得到磺酰基稳定的环氧乙烷基阴离子，再与三氟甲磺酸酯（triflate）反应，得到高产率的偶联产物. 6-内环化法合成聚四氢吡喃研究了反式稠合聚四氢吡喃的新合成方法。该方法涉及两个关键反应：（i）磺酰基稳定的环氧乙烷阴离子与三氟甲磺酸酯的烷基化，（ii）在吸电子磺酰基的辅助下，酸促进所得羟基环氧砜的6-内环化.甲基取代的六元环醚的合成基于甲基取代的羟基环氧砜的6-内环化反应，发展了一种合成含甲基邻环氧的四氢吡喃的通用方法.半短鞭藻毒素B的合成半短鞭藻毒素B是从赤潮生物短裸藻（Gymatreinium breve）的培养细胞中分离得到的一种多环醚类海洋毒素，具有独特的6，6，7，7-四环醚环体系。采用环氧乙烷阴离子策略完成了半短鞭螺毒素B的全合成。

项目成果

Yuji Mori: "Reiterative Synthesis of trans-Fused Polytetrahydropyrans Using the Oxiranyl Anion."Chem.Eur.J.. Vol.3-No.6. 849-852 (1997)

Yuji Mori：“使用环氧乙烷基阴离子重复合成反式稠合聚四氢吡喃。”Chem.Eur.J. Vol.3-No.6。

森 裕二: "求核性エポキシドとしてのオキシラニルアニオンの発生と反応" 有機合成化学協会誌. 55. 26-35 (1997)

Yuji Mori：“作为亲核环氧化物的环氧乙烷基阴离子的生成和反应”合成有机化学学会杂志 55. 26-35 (1997)。

Yuji Mori: "Synthesis of (6S,7S,9R,10R)-6,9-Epoxynonadec-18-ene-7,10-diol, a Marine Epoxy Lipid Isolated from the Brown Alga, Notheia anomala, by an Oxiranyl Anion Strategy"Tetrahedron Letters. 40. 731-734 (1999)

Yuji Mori：“通过 Oxiranyl 阴离子策略合成 (6S,7S,9R,10R)-6,9-Epoxynonadec-18-ene-7,10-diol，这是一种从褐藻 Notheia anomala 中分离出来的海洋环氧脂质

Yuji Mori: "Synthesis of Methyl-Substituted trans-Fused Tetrahydropyrans via 6-endo Cyclization"Tetrahedron Letters. 40. 8019-8022 (1999)

Yuji Mori：“通过 6-内环化合成甲基取代的反式稠合四氢吡喃”四面体字母。

Yuji Mori: "Reiterative Synthesis of Trans-Fused Tetrahydropyrans Using Oxiranyl Anion" Chem.Eur.J. 3. 849-852 (1997)

Yuji Mori：“使用环氧乙烷基阴离子重复合成反式稠合四氢吡喃”Chem.Eur.J。