Development of determination method of absolute configuration using binaphthyl CD probe and its application to natural products

联萘CD探针绝对构型测定方法的建立及其在天然产物中的应用

• 批准号: 23590027
• 负责人: HOSOI shinzo
• 金额: $ 3.33万
• 依托单位: Kyoto Pharmaceutical University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2011
• 资助国家: 日本
• 起止时间: 2011 至 2013
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-23590027/
• 关键词: 誘起円二色性; ビナフチル; 絶対配置決定法; キラルアミン; 立体配座解析; ステロール; 天然物; キラル二級アルコール; 円二色性; ＣＤプローブ; 絶対配置決定; アシルシアニド; 誘起ＣＤ

The induced circular dichroism (ICD) method was proven to be practical and applicable to natural products: 1) various types of unsaturated sterols were hydrogenated to give saturated sterols. As a result, CD spectra of the binaphthyl derivatives of the saturated sterols showed bisignate curves centered at 240 nm (3S: positive chirality; 3R: negative one). This should contribute significantly to the analysis of metabolites of various types of sterols. 2) a novel CD chromophoric agent having two reaction sites was designed and applied to chiral secondary alcohols. The intensity of Cotton effects was found to be twice more than that of the monoester. 3) its application to D, L-cycloserines was examined: D-cycloserine derivative with an (R)-configuration showed positive exciton chirality whereas the L-cycloserine derivative with an (S)-configuration exhibited a negative one. It will be a powerful tool to determine the absolute configurations of various natural products with an amino group.

诱导圆二色性（ICD）方法被证明是实用且适用于天然产物的：1）将各种类型的不饱和甾醇氢化得到饱和甾醇。结果表明，饱和甾醇的联萘衍生物的CD光谱显示出以240 nm为中心的双信号曲线（3S：正手性; 3R：负手性）。这将大大有助于分析代谢产物的各种类型的甾醇。2)设计了一种具有两个反应位点的新型CD发色剂，并将其应用于手性仲醇。发现棉效应的强度是单酯的两倍。3)考察了其对D，L-环丝氨酸的应用：具有（R）-构型的D-环丝氨酸衍生物显示正激子手性，而具有（S）-构型的L-环丝氨酸衍生物显示负激子手性。这将是一个强有力的工具，以确定各种天然产物的绝对构型的氨基。

项目成果

Induced circular dichroism in chiral N-methyl amides possessing an achiral binaphthyl chromophore and its application to absolute configuration determination of aliphatic chiral amines

• DOI: 10.1016/j.tetasy.2012.06.013
• 发表时间: 2012-07-15
• 期刊: TETRAHEDRON-ASYMMETRY
• 作者: Fujiwara, Toshio;Taniguchi, Yuka;Hosoi, Shinzo
• 通讯作者: Hosoi, Shinzo

誘起円二色性を基盤とするステロール類の3位水酸基の絶対配置決定について

基于诱导圆二色性测定甾醇3-羟基绝对构型

• 发表时间: 2012
• 作者: 冨士原聡夫;谷口由佳;岩崎宏樹;細井信造;山下正行
• 通讯作者: 山下正行

ビナフチル型新規CD発色試薬の開発とキラル第二級アルコールの絶対配置決定

新型联萘型CD显色剂的研制及手性仲醇绝对构型的测定

• 作者: 冨士原聡夫;細井信造
• 通讯作者: 細井信造

Novel approach to determining the absolute configurations at the C3-positions of various types of sterols based on an induced circular dichroism

基于诱导圆二色性确定各类甾醇 C3 位绝对构型的新方法

• 发表时间: 2012
• 期刊: Steroids
• 影响因子: 2.7
• 作者: Toshio Fujiwara;Yuka Taniguchi;Yukiteru Katsumoto;Takeyuki Tanaka;Minoru Ozeki;Hiroki Iwasaki;Manabu Node;Masayuki Yamashita;Shinzo Hosoi
• 通讯作者: Shinzo Hosoi

ビナフチル型新規CD発色試薬の開発とキラル第二級アルコールの絶対配置決定法への応用

新型联萘型CD显色剂的研制及其在手性仲醇绝对构型测定方法中的应用

• 发表时间: 2013
• 作者: 金子聡;長津心;大久保綾美;高取和彦;長岡博人;河野大貴,冨士原聡夫,谷口由佳,村木加愉子,國立悠里,馬場ゆうみ,岩﨑宏樹,小島直人,細井信造,山下正行
• 通讯作者: 河野大貴,冨士原聡夫,谷口由佳,村木加愉子,國立悠里,馬場ゆうみ,岩﨑宏樹,小島直人,細井信造,山下正行