Synthesis of enzyme mimic dual activation catalyst and its application for asymmetric synthesis

模拟酶双重活化催化剂的合成及其在不对称合成中的应用

• 批准号: 17550098
• 负责人: YAMAMOTO Iwao
• 金额: $ 2.3万
• 依托单位: SHINSHU UNIVERSITY
• 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: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-17550098/
• 关键词: asymmetric synthesis; synthetic enzyme; dual activation catalyst; bisoxazoline; 不斉シアノアリル化反応; 不斉シアノシリル化反応

The asymmetric allylation reactions of aldehydes catalyzed by a 10 mol% bisoxazoline complex bearing a phosphine oxide moiety(PM-Box), which was newly designed and synthesized from L-serine, afforded the corresponding homoallylic alcohols in 48-74% yields with 39-86% ee. The reaction proceeds with the dual activation of the aldehyde and allylsilane by the Lewis acid and base of the catalyst. The evidence for the activation of the allylsilane was clarified by the ^<31>P NMR spectra.The PM-Box-Cu(OTf)2 complex worked effectively in asymmetric reaction of imines with trimethylsilylsilane. For example, a reaction of benzylidene-N-benzhydrilimene with trimethylsilylsilane in the presence of 3mol% of PM-Box-Cu(OTf)2 gave a corresponding homoallyl amine in 91% yield with 90%ee. Furthermore, Strecker reactions of ketimines in the presence of 3mol% of the catalyst afford the product up to 96%ee.

醛的不对称烯丙基化反应由10 mol％的双唑唑啉复合物催化，带有磷酸氧化物部分（PM-box），该部分是由L秒新设计和合成的，可提供48-74％的同型同型醇，其产量为39-86％EE。反应以甲醛和催化剂的碱基对醛和烯丙基硅烷的双重激活进行。通过 ^<31> P NMR光谱阐明了烯丙基烷激活的证据。PM-box-Cu（OTF）2复合物在亚胺与三甲基二甲硅烷的不对称反应中有效起作用。例如，在存在3mol％PM-box-Cu（OTF）2的情况下，苯基二烯-N-苯二二二二烯与三甲基二甲硅烷的反应给出了91％的同酰胺胺，EE为91％。此外，在存在3mol％催化剂的情况下，酮胺的茎反应可为EE提供高达96％的EE。

项目成果

Enantioselective Allylation Allylation of Aldehydes Catalyzed by New Bifunctonal Bisoxazoline-metal Complexes

新型双功能双恶唑啉-金属配合物催化醛的对映选择性烯丙基化

• 期刊: Tetrahedron (未定)(印刷中)
• 作者: 竹内敬一;武田琢磨;藤本哲也;山本巖
• 通讯作者: 山本巖