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.

以l -丝氨酸为原料，设计合成了含氧化膦的10 mol%双唑啉配合物（mp - box），催化醛类的不对称烯丙基化反应，产率为48 ~ 74%，ee为39 ~ 86%。催化剂的路易斯酸和路易斯碱使醛和烯丙基硅烷双重活化。烯丙基硅烷活化的证据被^<31>P核磁共振谱所证实。PM-Box-Cu(OTf)2配合物在亚胺与三甲基硅基硅烷的不对称反应中表现良好。例如，在3mol%的PM-Box-Cu(OTf)2存在下，苄基- n -苯并二苯胺与三甲基硅基硅烷反应得到了产率91%、ee 90%的同丙烯胺。此外，在3mol%的催化剂存在下，氯胺酮的streker反应可使产物达到96%的ee。

项目成果

Enantioselective allylation of aldehydes catalyzed by new bifunctional bisoxazoline–metal complexes

• DOI: 10.1016/j.tet.2007.02.104
• 发表时间: 2007-06
• 期刊: Tetrahedron
• 影响因子: 2.1
• 作者: K. Takeuchi;Takuma Takeda;T. Fujimoto;I. Yamamoto

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