Construction of Carbon Skeleton via Lipase-Catalyzed Domino-Type Syntheses with Dynamic Kinetic Resolution
通过脂肪酶催化的多米诺骨牌动态分辨率合成碳骨架的构建
基本信息
- 批准号:17590006
- 负责人:
- 金额:$ 2.24万
- 依托单位:
- 依托单位国家:日本
- 项目类别:Grant-in-Aid for Scientific Research (C)
- 财政年份:2005
- 资助国家:日本
- 起止时间:2005 至 2006
- 项目状态:已结题
- 来源:
- 关键词:
项目摘要
The lipase-catalyzed organic syntheses have been gaining increased attention as environmentally benign processes recently. However, their use has been limited mainly for the preparation of optically active compounds via the kinetic resolution of racemic alcohols, and their application to the construction of carbon skeleton are few. Recently, we disclosed the first domino-type asymmetric synthesis, in which the lipase-catalyzed kinetic resolution of racemic alcohols with functionalized ethoxyvinyl esters was followed by the intramolecular cycloaddition reaction of the resulting optically active esters to directly give polycyclic compounds. We also developed some ruthenium complexes that effectively catalyze the racemization of optically active alcohols at room temperature. The combination of the ruthenium complexes and lipases have achieved the first domino-type synthesis accompanied by a dynamic kinetic resolution (DKR). This project has aimed at the practical expansion of this domino- … More type synthetic methodology. The followings are summary of the results:1. A novel DKR of secondary allyl alcohols has been developed by the combined use of the oxovanadium compound, VO(OSiPh_3)_3, and the lipases to give optically active allyl esters (88-99% ee) in 69-99% isolated yields. This method features the unique racemization process through the vanadium-catalyzed 1,3-transposition of the allyl alcohols.2. The developed racemization enabled an unprecedented DKR of the tertiary allyl alcohols with the migration to give the same products with better optical purity; viz., 99% ee, in most cases. These results have shown that the structural isomers of two kinds of allyl alcohols can be equally employed for this DKR and offer a new convenient strategy for the asymmetric synthesis of optically pure allyl acetates. The application of these methods to the allyl alcohols having a diene moiety is now under study in our laboratory, which is expected to construct the carbon skeleton via the domino-type process.3. Studies for the development of more potent metal catalysts to accelerate the above-mentioned racemization process have been carried out, and some molybdenum compounds were discovered as potential candidates. Less
近年来,脂肪酶催化的有机合成作为一种环境友好的合成方法受到了广泛的关注。然而,它们的应用主要局限于通过外消旋醇的动力学拆分来制备光学活性化合物,并且它们在碳骨架构建中的应用很少。最近,我们公开了第一个多米诺骨牌型不对称合成,其中脂肪酶催化的动力学拆分外消旋醇与官能化乙氧基乙烯基酯,随后通过分子内环加成反应得到的光学活性酯,直接得到多环化合物。我们还开发了一些钌配合物,在室温下有效地催化光学活性醇的外消旋反应。钌配合物和脂肪酶的结合实现了第一个多米诺骨牌式的合成伴随着动态动力学拆分(DKR)。该项目旨在实际扩大这一多米诺骨牌- ...更多信息 类型综合方法学主要研究结果如下:1.本文报道了一种新的仲烯丙醇的DKR反应,它是由氧钒化合物VO(OSiPh_3)_3和脂肪酶联合使用,以69-99%的分离收率得到光学活性的烯丙基酯(88- 99%ee)。该方法的特点是通过钒催化烯丙醇的1,3-转座反应进行独特的消旋过程.所开发的外消旋化使得叔烯丙基醇的具有迁移的前所未有的DKR能够得到具有更好光学纯度的相同产物;即,99%ee,在大多数情况下。这些结果表明,两种烯丙醇的结构异构体可以同等地用于该DKR,并为光学纯乙酸烯丙酯的不对称合成提供了一种新的方便的策略。本实验室正在研究这些方法在含双烯结构的烯丙醇中的应用,有望通过多米诺式的过程构建碳骨架.已经进行了开发更有效的金属催化剂以加速上述外消旋化过程的研究,并且发现了一些钼化合物作为潜在的候选物。少
项目成果
期刊论文数量(17)
专著数量(0)
科研奖励数量(0)
会议论文数量(0)
专利数量(0)
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AKAI Shuji其他文献
AKAI Shuji的其他文献
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{{ truncateString('AKAI Shuji', 18)}}的其他基金
Synthesis of PEGylated drug candidates for PET imaging
用于 PET 成像的聚乙二醇化候选药物的合成
- 批准号:
24659049 - 财政年份:2012
- 资助金额:
$ 2.24万 - 项目类别:
Grant-in-Aid for Challenging Exploratory Research
Nucleophilic deoxyfluorination of phenol derivatives and its application to drug discovery
苯酚衍生物的亲核脱氧氟化及其在药物发现中的应用
- 批准号:
24390005 - 财政年份:2012
- 资助金额:
$ 2.24万 - 项目类别:
Grant-in-Aid for Scientific Research (B)
The development of innovative asy mmetric synthetic methods by the enzyme-metal combo catalysis
酶-金属组合催化创新不对称合成方法的发展
- 批准号:
21390005 - 财政年份:2009
- 资助金额:
$ 2.24万 - 项目类别:
Grant-in-Aid for Scientific Research (B)
Development of regioselective reactions of substituted benzynes and its application to synthesis of polysubstituted fused aromatic compounds
取代苯炔区域选择性反应的进展及其在多取代稠合芳香族化合物合成中的应用
- 批准号:
19590008 - 财政年份:2007
- 资助金额:
$ 2.24万 - 项目类别:
Grant-in-Aid for Scientific Research (C)
Development of Lipase-Catalyzed Domino-Type Asymmetric Syntheses
脂肪酶催化多米诺骨牌型不对称合成的发展
- 批准号:
15590005 - 财政年份:2003
- 资助金额:
$ 2.24万 - 项目类别:
Grant-in-Aid for Scientific Research (C)
Development of New Method for Construction of Chiral, Non-Racemic Quaternary Carbon Center by Enzymatic Acylation of Alcohols and Application Thereof
醇酶酰化构建手性非外消旋季碳中心新方法的开发及其应用
- 批准号:
13672214 - 财政年份:2001
- 资助金额:
$ 2.24万 - 项目类别:
Grant-in-Aid for Scientific Research (C)
Development of Lipase-Catalyzed, Effective, Asymmetric Synthetic Methods
脂肪酶催化、有效、不对称合成方法的开发
- 批准号:
11672102 - 财政年份:1999
- 资助金额:
$ 2.24万 - 项目类别:
Grant-in-Aid for Scientific Research (C)