New Strategy for Determining the Absolute Stereochemistry of Mono-Functional Natural Products by the CD Exciton Chirality Method
CD激子手性法测定单功能天然产物绝对立体化学的新策略
基本信息
- 批准号:11480159
- 负责人:
- 金额:$ 9.47万
- 依托单位:
- 依托单位国家:日本
- 项目类别:Grant-in-Aid for Scientific Research (B)
- 财政年份:1999
- 资助国家:日本
- 起止时间:1999 至 2002
- 项目状态:已结题
- 来源:
- 关键词:
项目摘要
1. We have developed a new strategy for determining the absolute configuration of mono-fucntional compounds by the CD exciton chirality method. This method is powerful for the absolute configurational studies of chiral compounds including natural products.2. We have recently developed two "powerful chiral acids" for enantioresolution of various alcohols by HPLC on silica gel and also for determination of their absolute configurations by X-ray crystallography and/or by the 1H NMR anisotropy method. The first is the chiral dichlorophthalic acid (-)-1, which was reacted with racemic alcohol to give a diastereomeric mixture of esters. The mixture of esters obtained was separated by HPLC on silica gel, and two separated esters were crystallized respectively to afford single crystals suitable for X-ray analysis. The absolute configuration of the alcohol part was determined by X-ray crystallography of the esters, and enantiopure alcohols were easily recovered by solvolysis with K_2CO_3 in methanol.3. The second powerful chiral acid is 2-methoxy-2-(1-naphthyl)propionic acid (MαNP acid, (S)-(+)-2 or R-(-)-2) for determining the absolute configuration of chiral alcohols by the 1H NMR anisotropy method.The enantiopure MαNP acid (S)-(+)-2 was allowed to react with racemic alcohols yielding diastereomeric mixtures of esters, which were easily separated by HPLC on silica gel. The NMR signals of diastereomeric esters obtained were fully assigned by the various two-dimensional methods leading to the calculation of Δδ values (Δδ = δ(R,X)-δ(S,X)). By applying the MαNP sector rule, the absolute configuration X was determined. Separated esters were hydrolyzed with KOH/EtOH to recover enantiopure alcohols.4. Using MαNP acid, (S)-(+)-2 and its deuterium labeled enantiomer R-(-)-2-d_6, we have developed a new diastereomer method for determining enantiomeric excess (% ee) of chiral alcohols by MS spectrometry.
1. 我们开发了一种通过圆二色激子手性方法测定单功能化合物绝对构型的新策略。该方法对于包括天然产物在内的手性化合物的绝对构型研究具有强大的作用。 2.我们最近开发了两种“强手性酸”,用于通过硅胶上的 HPLC 对各种醇进行对映拆分,并通过 X 射线晶体学和/或 1 H NMR 各向异性方法测定其绝对构型。第一种是手性二氯邻苯二甲酸(-)-1,它与外消旋醇反应得到酯的非对映混合物。将获得的酯混合物通过硅胶HPLC分离,并将分离的两种酯分别结晶,得到适合X射线分析的单晶。通过酯的X射线晶体学测定了醇部分的绝对构型,并且通过K_2CO_3在甲醇中的溶剂解很容易回收对映体纯醇。 3.第二种强手性酸是 2-甲氧基-2-(1-萘基)丙酸(MαNP 酸,(S)-(+)-2 或 R-(-)-2),用于通过 1H NMR 各向异性方法测定手性醇的绝对构型。对映体纯 MαNP 酸 (S)-(+)-2 与外消旋醇反应,产生非对映异构体 酯的混合物,可以通过硅胶上的 HPLC 轻松分离。获得的非对映酯的 NMR 信号通过各种二维方法完全分配,从而计算 Δδ 值 (Δδ = δ(R,X)-δ(S,X))。通过应用MαNP扇区规则,确定了绝对构型X。分离的酯用KOH/EtOH水解回收对映体纯醇。4.利用 MαNP 酸 (S)-(+)-2 及其氘标记的对映体 R-(-)-2-d_6,我们开发了一种新的非对映体方法,通过质谱法测定手性醇的对映体过量 (% ee)。
项目成果
期刊论文数量(206)
专著数量(0)
科研奖励数量(0)
会议论文数量(0)
专利数量(0)
原田宣之: "化学が拓くナノテクノロジー「光で回転する分子モーター」をつくる"化学. 57. 31-34 (2002)
Nobuyuki Harada:“创造化学开发的纳米技术:‘随光旋转的分子马达’”,Chemistry 57. 31-34 (2002)。
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N.Berova, N.Harada: "'Electronic Spectroscopy : Exciton Coupling, Theory and Applications, Exciton Coupled Circular Dichroism,'in J.Lindon, G.Tranter, and J.Holmes, Ed, "Encyclopedia of Spectroscopy & Spectrometry""Academic Press Ltd, London. 19 (2000)
N.Berova、N.Harada:“‘电子光谱:激子耦合、理论与应用、激子耦合圆二色性’,载于 J.Lindon、G.Tranter 和 J.Holmes,Ed,《光谱百科全书》
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P.Kutschy, N.Harada: "Spirocyclization Strategy toward Indole Phytoalexyins.The First Synthesis of (±)-1-Methoxyspirobrassinin, (±)-1-Methoxyspirobrassinol and (±)-1-Methoxyspirobrassinol Mthyl Ether"Tetrahedron Lett.. 43. 9489-9492 (2002)
P.Kutschy,N.Harada:“吲哚植物抗毒素的螺环化策略。(±)-1-甲氧基螺油菜素、(±)-1-甲氧基螺油菜素和(±)-1-甲氧基螺油菜素甲醚的首次合成”四面体快报.. 43 .9489-9492 (2002)
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T.Nehira, N.Harada: "Circular Dichroisn and Absolute Stereochemistry of 〔8〕Paracyclophane-10-carbonitrile and Related Compounds"Enantiomer. 5. 139-144 (2000)
T. Nehira、N. Harada:“[8] Paracyclophane-10-carbonitrile 及相关化合物的圆二色性和绝对立体化学”对映体 5. 139-144 (2000)。
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S.Nishimura, N.Harada: "Corticatic Acids D and E, Polyacetylenic Gerranylgeranyltransferase Type I Inhibitors, from the Marine Sponge Petrosia corticata"J.Natural Products. 65. 1353-1356 (2002)
S.Nishimura,N.Harada:“皮质酸 D 和 E,聚乙炔香叶基香叶基转移酶 I 型抑制剂,来自海洋海绵 Petrosia corticata”J.Natural Products。
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HARADA Nobuyuki其他文献
HARADA Nobuyuki的其他文献
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{{ truncateString('HARADA Nobuyuki', 18)}}的其他基金
Employment and Technology in SMEs and Revitalization of the Japanese Economy
中小企业的就业和技术与日本经济的振兴
- 批准号:
26380286 - 财政年份:2014
- 资助金额:
$ 9.47万 - 项目类别:
Grant-in-Aid for Scientific Research (C)
Drastic Changes in the Economic Environment and the Role of SMEs
经济环境的剧变与中小企业的作用
- 批准号:
23730268 - 财政年份:2011
- 资助金额:
$ 9.47万 - 项目类别:
Grant-in-Aid for Young Scientists (B)
The Development of Coaching Ability Criterion for Cooperative Learning
合作学习辅导能力标准的制定
- 批准号:
22530814 - 财政年份:2010
- 资助金额:
$ 9.47万 - 项目类别:
Grant-in-Aid for Scientific Research (C)
Small Business and Entrepreneurship in the Shrinking Economy
经济萎缩中的小企业和创业精神
- 批准号:
20730176 - 财政年份:2008
- 资助金额:
$ 9.47万 - 项目类别:
Grant-in-Aid for Young Scientists (B)
A Study of Cultural Legends in the Ryukyu Islands
琉球群岛文化传说研究
- 批准号:
19520180 - 财政年份:2007
- 资助金额:
$ 9.47万 - 项目类别:
Grant-in-Aid for Scientific Research (C)
The development of a build-up program to foster teachers instructing competences by improving "classroom-learning community"
制定培养计划,通过改善“课堂学习社区”来培养教师教学能力
- 批准号:
19530688 - 财政年份:2007
- 资助金额:
$ 9.47万 - 项目类别:
Grant-in-Aid for Scientific Research (C)
A study of heroic legends in the Ryukyu islands
琉球群岛英雄传说研究
- 批准号:
13610526 - 财政年份:2001
- 资助金额:
$ 9.47万 - 项目类别:
Grant-in-Aid for Scientific Research (C)
Development of CD Method and Application to Stereochemistry
CD方法的发展及其在立体化学中的应用
- 批准号:
10045022 - 财政年份:1998
- 资助金额:
$ 9.47万 - 项目类别:
Grant-in-Aid for Scientific Research (B).
Development of New CD Methods for Determining the Absolute Stereochemistry of Chiral Molecules
开发测定手性分子绝对立体化学的新 CD 方法
- 批准号:
10208202 - 财政年份:1998
- 资助金额:
$ 9.47万 - 项目类别:
Grant-in-Aid for Scientific Research on Priority Areas (B)
Research for the Development, Construction, and Management of the Chirality Database
手性数据库开发、建设与管理研究
- 批准号:
10554035 - 财政年份:1998
- 资助金额:
$ 9.47万 - 项目类别:
Grant-in-Aid for Scientific Research (B)