Development of Asymmetric Allylation Reaction Using Allygermanes

利用烯锗烷开发不对称烯丙基化反应

• 批准号: 10640528
• 负责人: AKIYAMA Takahiko
• 金额: $ 2.5万
• 依托单位: Gakushuin University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 1998
• 资助国家: 日本
• 起止时间: 1998 至 1999
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-10640528/
• 关键词: allylation; allylgermane; chemoselectivity; asymmetric synthesis; enantioselectivity; scandium triflate; アリル化; アルデヒド; ビナフトール; ホモアリルアルコール; 有機合成化学

We focused on organogermanium compounds, which have attracted little attention of synthetic organic chemists, in this project and studied on the allylation reactions of carbonyl compounds by means of allylgermanes.On treatment of aldehyde and tetraallylgermane in the presence of catalytic amount of scandium (III) triflate in aqueous acetonitrile, allylation of aldehyde proceeded smoothly to afford homoallylic alcohols in excellent yields.For the allylation of aldimines, allyitriethylgermane was found to be quite effective and scandium (III) triflate catalyzed allylation of aldimines in acetonitrile furnished homoallylic amines in high yields. Present allylation reaction showed high chemoselectivity toward aldimines in preference to aldehyde. Thus, three component synthesis of homoallylic amines from aidehyde, amine, and allylgermane proceeded smoothly to afford homoallylic amines in good yields.It was found that activation of aldimines was achieved by the combination of BFィイD23ィエD2・OetィイD22ィエD2 and CHィイD23ィエD2 COィイD22ィエD2 H, which are cheaper and easier to handle than scandium (III) triflate.Next, enantioselective allylation of aldehyde with allylgermane was studied. Allylation of aldehyde took place highly enantioselectively by means of a chiral catalyst, derived from R-(+)-binaphthol and titanium tetraisopropoxide, to afford homoallylic alcohols as high as 89% ee. This is the first enantioselective reactions by use of allylgermanes as allylic organometallics.

本课题以有机锗化合物为研究对象，对合成有机化学家较少关注的有机锗化合物进行了烯丙基锗的烯丙化反应研究。在乙腈水溶液中，在三氟化钪的催化下，醛和四烯丙基锗的烯丙化反应顺利进行，得到了高产率的高烯丙基醇。在乙二胺的烯丙化反应中，三氟化钪催化乙腈中醛亚胺的烯丙化反应以较高的产率得到高烯丙胺。目前的烯丙化反应显示出对乙二胺的高化学选择性，而不是醛。因此，以醛、胺和烯丙基锗为原料合成高烯丙基胺的反应进展顺利，得到了高烯丙基胺的高烯丙基胺。研究发现，乙二胺的活化是通过BFィイD23ィエD2·OetィイD22ィエD2和CHィイD23ィエD2 COィイD22ィエD2H的组合实现的，这两种反应比三氟化钪更便宜、更容易操作。以R-(+)-联苯酚和四异丙氧基钛为原料，在手性催化剂作用下，醛的烯丙化反应具有很高的对映选择性，可得到高达89%ee的高烯丙醇。这是首次使用烯丙基有机金属化合物进行的对映选择性反应。

项目成果

T.Akiyama, J.Iwai, Y.Onuma, and H.kagoshima: "Chemoselective Allylation of Aldimine with Allytriethylgermane By the Combined Use of BFィイD23ィエD2・OetィイD22ィエD2 and CHィイD23ィエD2COィイD22ィエD2H"J. Chem. Soc., Chem. Commun.. 2191-2192 (1999)

T.Akiyama、J.Iwai、Y.Onuma 和 H.kagoshima：“结合使用 BF D23 D2·Oet D22 D2 和 CH D23 进行醛亚胺与烯丙基三乙基锗烷的化学选择性烯丙基化” J. Chem. Soc., Chem. Commun. 2191-2192 (1999)

Takahiko Akiyama: "Scandium Trifluoromethane sulfonate-Catalyzed Chemoselective Allylatin Reactions of Carbonyl Compounds with Tetraallylgermane in Aqueous Media"Tetrahedron. 55・24. 7499-7508 (1999)

Takahiko Akiyama：“三氟甲磺酸钪催化的羰基化合物与四烯丙基锗烷在水介质中的化学选择性烯丙基反应”Tetrahedron 55・24（1999）。

Takahiko Akiyama: "Scandium Trifluoromethanesulfonate-Catalyzed Chemoselective Allylation Reactions of Carbonyl Compounds with Tetraallylgermane in Aqueous Media"Tetrahedron. 55. 7499-7508 (1999)

Takahiko Akiyama：“三氟甲磺酸钪催化的羰基化合物与四烯丙基锗烷在水介质中的化学选择性烯丙基化反应”四面体。

Takahiko Akiyama: "Chemoselective Allylation of Aldimine with Allyltriethylgermane By the Combined Use of BF_3・OE_<t2> and CH_3CO_2H"J. Chem. Soc., Chem. Commun.. 2191-2192 (1999)

Takahiko Akiyama：“结合使用 BF_3·OE_<t2> 和 CH_3CO_2H 进行醛亚胺的化学选择性烯丙基化”J. Chem.，Chem. 2191-2192

T.Akiyama, J.Iwai and M..Sugano: "Scandium Trifluoromethanesulfonate-Catalyzed Chemoselective Allylation Reactions of Carbonyl Compounds with Tetraallylgermane in Aqueous Media"Tetrahedron. 55. 7499-7508 (1999)

T.Akiyama、J.Iwai 和 M..Sugano：“三氟甲磺酸钪催化的羰基化合物与四烯丙基锗烷在水介质中的化学选择性烯丙基化反应”四面体。