CHEMOSELECTION CONTROL OF DIELSALDER REACTIONS USING TWO CONJUGATE DIENES

使用两种共轭二烯对迪尔萨尔德反应进行化学选择控制

• 批准号: 13555248
• 负责人: KANEMASA Shuji
• 金额: $ 8.83万
• 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: 2001
• 资助国家: 日本
• 起止时间: 2001 至 2002
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-13555248/
• 关键词: Diels-Alder reaction; chemoselectivity; conjugate diene; Lewis acid; catalytic activation; halonium ion; dipolar cycloaddition; nitrone; 共役ジエン; 官能基選択性制御; アルケンの直接活性化

Establishment of a synthetic method for chemoselectivity control in Diels-Alder reactions using two kinds of conjugate dienes, both of which can act as dienes and dienophiles depending upon the reaction conditions. Two possible combinations are possible for the chemoselectivity, and other selectivities such as regio- and diastereoselectivities. We have investigated the reactions using two different conjugate dienes, such as acyclic and cyclic ones, in the presence of a variety of catalysts.2-Methyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, and cyclopentadiene have been selected as conjugate 1,3-dienes; nucleophiles such as the same 1,3-dienes and nitrones as 1,3-dipole have been used.. For the Diels-Alder reactions using these conjugate dienes and nitrone dipolar cycloadditions toward these conjugate dienes, a variety of Lewis acid catalysts such as halogens themselves, halonium ions having noncordinating halonium ions, N-haloammonium and N-halopyridinium salts have been applied in catalytic amounts. However, these catalysts are all ineffective for the activation.Silyl cations, sulfonium cations, and selenium cations, which have been generated in situ by interaction of the corresponding halide derivatives with silver borontetrafluoride, have failed to accelerated the reactions. Allylic cation species have been generated from allylic acetates and carbonates in the presence of palladium zero catalysts and allowed to react with conjugate dienes and nitrones. However, no specific effect has not been observed.

使用两种共轭二烯建立了在DIELS-ALDER反应中进行化学选择性控制的合成方法，这两种方法都可以用作二烯和二氧化碳，具体取决于反应条件。对于化学选择性以及其他选择性，例如区域和非映射性，可能有两种可能的组合。我们已经在存在多种催化剂的情况下使用了两种不同的偶联二烯，例如循环和环状二烯。已使用了与1,3-偶极相同的1,3-二烯和硝基等的接核者。 N-甲吡吡丁盐已经以催化量施用。然而，这些催化剂在激活中均无效。silyl阳离子，磺基阳离子和硒阳离子，这些催化剂通过相应的卤化衍生物与银硼氟氟氟化物的相互作用而在原位产生，但未能加速这些反应。在钯零催化剂的存在下，已经从烯丙基乙酸盐和碳酸盐中产生了烯丙基阳离子物种，并允许与结合二enes和硝酸酮反应。但是，尚未观察到没有特定效果。

项目成果

K.Nakama, S.Seki, S.Kanemasa: "Enantioselective Conjugate Additions of Aldoximes to 3-Crotonoyl-2-oxazolidinone and 1-Crotonoyl-3-phenyl-2-imidazolidinone Catalyzed by the Aqua Complex between R, R-DBFOX/Ph and Zinc(II) Perchlorate"Tetrahedron Lett. 43,5.

K.Nakama、S.Seki、S.Kanemasa：“由 R、R-DBFOX/ 之间的水复合物催化醛肟与 3-巴豆酰基-2-恶唑烷酮和 1-巴豆酰基-3-苯基-2-咪唑烷酮的对映选择性共轭加成”

Akio Kamimura, Yukio Kaneko, Ayaki Ohta, Kenji Matsuura, Yasuo Fujimoto, Akikazu Kakehib, Shuji Kanemasa: "Enantioselective preparation of 3, 4, 5-trisubstituted 4, 5-dihydroisoxazoles and their stereoselective elaboration of 5-side chain"Tetrahedron. 58(

Akio Kamimura、Yukio Kaneko、Ayaki Ohta、Kenji Matsuura、Yasuo Fujimoto、Akikazu Kakehib、Shuji Kanemasa：“3,4,5-三取代的 4,5-二氢异恶唑的对映选择性制备及其 5-侧链的立体选择性加工”四面体。

S.Kanemasa: "Effect of external reagents"Synthetic Application of 1,3-Dipolar Cycloaddition Chemistry Toward Heterocycles and Natural Products. 2002. 755-815 (2002)

S.Kanemasa：“外部试剂的影响”1,3-偶极环加成化学在杂环和天然产物中的合成应用。

S.Kanemasa, N.Ueno, M.Shirahase: "Nitrone Cycloaddition Reactions to a, b-Unsaturated carbonyl Acceptors Catalyzed by a Pinhole Lewis Acid Catalyst. Dramatic Rate Acceleration and Improvement of Regioselectivity and Diastereoselectivity"Tetrahedron Lett.

S.Kanemasa、N.Ueno、M.Shirahase：“针孔路易斯酸催化剂催化的 a, b-不饱和羰基受体的硝酮环加成反应。区域选择性和非对映选择性的显着速率加速和改进”Tetrahedron Lett。

S. Kanemasa, N.Ueno, M.Shirahase: "Nitrone Cycloaddition Reactions to a,b-Unsaturated carbonyl Acceptors Catalyzed by a Pinhole Lewis Acid Catalyst. Dramatic Rate Acceleration and Improvement of Regioselectivity and Diastereoselectivity"Tetrahedron Lett..

S. Kanemasa、N.Ueno、M.Shirahase：“针孔路易斯酸催化剂催化的 a,b-不饱和羰基受体的硝酮环加成反应。显着的速率加速以及区域选择性和非对映选择性的改进”Tetrahedron Lett..