CREATION OF TRIDENTATE TRANS-CHELATING CHIRAL LIGAND BASED ON A NEW MOLECULAR STRUCTURE DESIGN

基于新分子结构设计的三齿反螯合手性配体的构建

• 批准号: 09450343
• 负责人: KANEMASA Shuji
• 金额: $ 8.58万
• 依托单位: KYUSHU UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 1997
• 资助国家: 日本
• 起止时间: 1997 至 1998
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-09450343/
• 关键词: chiral Lewis acid catalyst; tridentate trans-chelating ligand; bisoxazoline ligand; chiral amplification; Diels-Alder reaction; nitrone cycloaddition; diazo cycloaddition; thiol conjugate addition; 3座トランス配位型配位子; ジベンゾフラン; 第1系列還位金属過塩素酸塩; 第1系列遷移金属

Establishment of a useful method of chirality control in catalyzed asymmetric reactions is one of the central subjects in the field of synthetic organic chemistry in 21st century. In the present research, we have designed and synthesized a new trans-chelating tridentate chiral ligand which has a dibenzofuran skeleton having two oxazoline substituents at 4- and 6-positions. From the study of a wide variety of asymmetric reactions catalyzed by the transition metal complexes of this new ligand, 4,6-dibenzofurandiyl-2,2-bis(4-phenyloxazoline) designated hereafter as DBFOXIPh, new findings as well as useful informations have been obtained as shown below :1. DBFOX/Ph Ligand forms stable complexes with the transition metal ions such as Mn(II), Fe(II), Co(II), Ni(II), Cu(II), Zn(lI) perchlorate hexahydrates. Some complexes can be isolated and show high catalytic activity as Lewis acids.2. The aqua nickel(II) complex of DBFOX/Ph ligand can be stored for months in air under moisture conditions w … More ithout loss of catalytic activity.3. The nickel complex catalyzes the Diels-Alder reactions between cyclopentadiene and 3-acryloyl-2-oxazotidinone to show the absolute endo selectivity and enantioselectivity.4. Aqua complexes show even higher levels of enantioselectivity and catalytic activity than the anhydrous complexes.5. The nickel and zinc complexes show extremely effective chiral amplification in the catalyzed Diels-Alder reactions.6. Two mechanisms have been proposed : (1) the precipitation of inert mesa 2 : 1 complex in the preparation stage of catalyst, (2) the heterochiral aggregation of 1 : 1 complexes is more stable than the homochiral aggregation.7. The aggreagtion of 1 : 1 complexes is based on the hydrogen bonding working between the water ligand and the perchiorate ions..8. The nickel complex shows sufficiently high catalytic activity in the reaction medium containing coordinating additives such as water, alcohols, carboxylic acids, and amines.9. The nickel and zinc complexes work as excellent catalysts in the nitrone cycloadditions using 3-crotonoyl-2-oxazolidinone to show the absolute endo selectivity and enantioselectivity.10. The zinc complex works as excellent catalyst in the diazo cycloadditions to 3-crotonoyl-2-oxazolidinone to show the absolute enantioselectivity, On the other hand, the magnesium complex is the best in the reaction of 3-crotonoyl-4,4-dimethyl-2-oxazolidinone where the mode of enantioselectivity is completely reversed. This result offers an interesting example of "ligand - auxiliary coorperative stereo control".11. The nickel complex catalyzes the conjugate addition of thiols to 3-crotonoyl-2-oxazolidinone to produce the conjugate adducts in high enantioselectivities. Less

建立一种有效的催化不对称反应手性控制方法是21世纪合成有机化学领域的中心课题之一。在本研究中，我们设计并合成了一种新型的反式螯合三齿手性配体，其骨架为二苯并呋喃，在4-位和6-位分别有两个恶唑啉取代基。通过对这一新配体的过渡金属络合物催化的各种不对称反应的研究，得到了新的发现和有用的信息如下：1.DBFOX/Ph配体与过渡金属离子如Mn(II)、Fe(II)、Co(II)、Ni(II)、Cu(II)、Zn(Li)形成稳定的络合物。一些配合物可以被分离出来，并表现出很高的催化活性，如路易斯酸。水镍(II)络合物在…的潮湿条件下，可在空气中保存数月更多而不损失催化活性。镍配合物催化环戊二烯与3-丙烯酰基-2-恶唑二酮的Diels-Alder反应，表现出绝对的内切选择性和对映选择性。水络合物表现出比无水络合物更高的对映体选择性和催化活性。镍和锌配合物在催化的Diels-Alder反应中表现出非常有效的手性放大作用。提出了两种机理：(1)催化剂制备阶段惰性台面2：1络合物的沉淀；(2)1：1络合物的异手性聚集比均手性聚集更稳定。1：1络合物的聚集是基于水配体与高氯酸盐离子之间的氢键作用。在含有水、醇、羧酸和胺等配位添加剂的反应介质中，镍配合物表现出足够高的催化活性。镍和锌配合物在3-巴豆酰基-2-恶唑烷酮的硝酮环加成反应中表现出绝对的内切选择性和对映体选择性。在3-巴豆酰基-2-恶唑烷酮的重氮环加成反应中，锌络合物表现出绝对的对映选择性，而镁络合物在3-巴豆酰基-4，4-二甲基-2-恶唑烷酮的重氮环加成反应中表现出最好的催化性能，其对映体选择性模式完全相反。这一结果为“配基-辅助协同立体控制”提供了一个有趣的例子。镍络合物催化硫醇与3-巴豆酰基-2-恶唑烷酮的共轭加成反应，生成具有高对映选择性的共轭加合物。较少

项目成果

S.Kanemasa,Y.Oderaotoshi, J.Tanaka,E.Wada: "Highly endo-and Enantioselective Asymmetric Nitrone Cycloadditions Catalyzed by the Aqua Complex of 4,6-Dibenzofurandiyl- 2,2-bis(4-phenyloxazoline)-Nicke(II) Perchlorate.Transition Structure Based on Dramatic E

S.Kanemasa、Y.Oderaotoshi、J.Tanaka、E.Wada：“4,6-二苯并呋喃二基-2,2-双(4-苯基恶唑啉)-Nicke 的水复合物催化的高度内切和对映选择性不对称硝酮环加成(

金政修司、大平落洋二: "遷移金属ルイス酸触媒を用いる不斉環状付加反応-触媒構造設計の新しい指針-" 有機合成化学協会誌. 56. 368-376 (1998)

Shuji Kanemasa、Yoji Ohirachi：“使用过渡金属路易斯酸催化剂的不对称环加成反应 - 催化剂结构设计的新指南”合成有机化学学会杂志 56. 368-376 (1998)。

S.Kanemasa,Y.Oderaotoshi,J.Tanaka, E.Wada: "Temperature Dependent H NMR Study of the Substrate Complex Derived from Zinc(H) Perchiorate,(R,R)-4,6-Dibenzofurandiyl-2,2- bis(4-phenylozaxoline),and 3-Acetyl-2- oxazolidinone.Evidence for Octahedral Structure

S.Kanemasa、Y.Oderaotoshi、J.Tanaka、E.Wada：“源自高氯酸锌 (H) 高氯酸锌 (R,R)-4,6-二苯并呋喃二基-2,2- 的底物复合物的温度依赖性 1H NMR 研究

S.Kanemasa,Y.Oderaotoshi,S.Sakaguchi,H.Yamamoto,J.Tanaka,E.Wada,D.P.Curran: "Transition Metal Aqua Complexes of Cationic Aqua Complexes of 4,6-Dibenzofuradiyl-2,2'-bis(4-phenyloxazoline)DBFOX/Ph.Effective Catalysis in Diels-Alder Reactions Showing Excelle

S.Kanemasa，Y.Oderaotoshi，S.Sakaguchi，H.Yamamoto，J.Tanaka，E.Wada，D.P.Curran：“4,6-二苯并呋喃基-2,2-双（的阳离子水配合物的过渡金属水配合物）

S.Kanemasa, Y.Oderaotoshi, J.Tanaka, E.Wada: "Highly endo- and Enantioselestive Asymmetric Nitrone Cycloadditions Catalyzed by the Aqua Complex of 4,6-Dibenzofurandiyl-2,2'-bis(4-phenyloxazoline)-Nickel(II)Perchlorate.Transition Structure Based on Dramati

S.Kanemasa、Y.Oderaotoshi、J.Tanaka、E.Wada：“4,6-二苯并呋喃二基-2,2-双(4-苯基恶唑啉)-镍的水复合物催化的高度内向和对映异构不对称硝酮环加成