Liquid Crystal Control of uni-to multi-molecular Thermal Reactions

单分子到多分子热反应的液晶控制

• 批准号: 13470496
• 负责人: KUNIEDA Takehisa
• 金额: $ 9.02万
• 依托单位: Kumamoto 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 2003
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-13470496/
• 关键词: Liquid crystal; Smectic phase; cholesteric phase; Intramolecular cycloaddition; Intermolecular cycloaddition; Mitsunobu reaction; Orientation regulation; スメクチック液晶; コレステリック液晶; 不斉アルキル化; 水素移動型不斉還元; 2-チアゾリン; 不斉Diels-Alder反応; 熱環化反応; 不斉機能化; 複素五員環

The aim of this research is to establish the new methodology for highly orientation-regulated reaction system using liquid crystal as medium, with regularity and fluidity. The following typical reactions have tried with a variety of liquid crystal medium :(1)Intramolecular [4+2] cycloaddition (unimolecular reaction) : Intramolecular uncatalyzed thermal cycloaddition reaction of trans-4-cyclohexylcyclohexyl decatrienoic acid esters in smectic liquid crystalline solvents such as bis(4-pentyloxyphenyl)trans-1,4-cyclohexanedicarboxylate (BPCD) was found to give bicyclic cycloadducts with extremely high diastereoselectivity and chemical yields, contrary to the poor results with isotropic medium such as 4-pentyloxyphenyl cyclohexanecarboxylate (PCC) and mesitylene.(2)Intermolecular [4+2] cycloaddition (bimolecular reaction) : Moderate stereoselectivities and reaction accerelation effect were observed for intermolecular cycloaddition with pyrroles and allene diesters in smectic medium.(3)Mitsunobu Reaction (tetramolecular reaction) : Unusual retention of the configuration of hydroxyl group of trans-4-substituted cyclohexanol by Mitsunobu reaction was observed in smectic medium, contrary to the usual result (inversion of configuration) in isotropic medium.

本研究旨在建立以液晶为介质，具有规整性和流动性的高度取向调控反应体系的新方法。在多种液晶介质中，尝试了以下典型反应：（1）分子内[4+2]环加成反应（单分子反应）：反式-4-环己基环己基癸三烯酸酯在近晶相液晶溶剂中的分子内非催化热环加成反应反式-1，4-环己烷二甲酸（4-戊氧基苯基）酯（BPCD）具有极高的非对映选择性和化学产率，与各向同性介质如环己烷羧酸4-戊氧基苯基酯（PCC）和均三甲苯的差结果相反。（2）分子间[4+2]环加成反应（双分子反应）：在近晶相介质中，吡咯和丙二烯二酯的分子间环加成反应具有中等的立体选择性和反应加速效应。（3）Mitsunobu反应（四分子反应）：在近晶相介质中观察到反式-4-取代环己醇羟基构型的异常保留，而在各向同性介质中观察到构型的反转。

项目成果

Alaa A-M Abdel-Aziz, J.Okuno, S.Tanaka, T.Ishizuka, H.Matsunaga, T.Kunieda: "An unusual enhancement of chiral induction by chiral 2-imidazolidinone auxiliaries."Tetrahedron Letters. 41. 8533-8537 (2000)

Alaa A-M Abdel-Aziz、J.Okuno、S.Tanaka、T.Ishizuka、H.Matsunaga、T.Kunieda：“手性 2-咪唑烷酮助剂对手性感应的不寻常增强。”四面体快报。

H.Matsunaga et al.: "Acceleration of ruthenium(II)-and rhodium(I)-catalyzed hydrogen-transfer reaction by rare earth metal triflates"Tetrahedron Lett.. 42. 8857-8859 (2001)

H.Matsunaga 等人：“稀土金属三氟甲磺酸盐加速钌 (II) 和铑 (I) 催化的氢转移反应”Tetrahedron Lett.. 42. 8857-8859 (2001)

T.Morita, Y.Nagasawa, S.Yahiro, H.Matsunaga, T.Kunieda: "Versatile Synthons for Optically Pure α-Amino Aldehydes and α-Amino Acids :(+)-and (-)-4,5-Dialkoxy-2-oxazolidinones"Organic Letters. 3. 897-899 (2001)

T.Morita、Y.Nagasawa、S.Yahiro、H.Matsunaga、T.Kunieda：“用于光学纯 α-氨基醛和 α-氨基酸：(+)-和 (-)-4,5-二烷氧基的多功能合成子-2-恶唑烷酮”《有机快报》。3. 897-899 (2001)

S.Hoshimoto, H.Matsunaga, T.Kunieda: "Sterically Constrained 'Roofed' 2-Thiazolidinones as Excellent Chiral Auxiliaries."Chem.Pharm.Bull.. 48. 1541-1544 (2000)

S.Hoshimoto、H.Matsunaga、T.Kunieda：“空间约束的‘屋顶’2-噻唑烷酮作为优秀的手性助剂。”Chem.Pharm.Bull.. 48. 1541-1544 (2000)

S.Hoshimoto et al.: "Highly Accelerating Effect of Lewis Acids on Ruthenium(II)-catalyzed Radical Addition Reactions"Chem.Pharm.Bull.. 50. 435-438 (2002)

S.Hoshimoto 等人：“路易斯酸对钌 (II) 催化的自由基加成反应的高度加速作用”Chem.Pharm.Bull.. 50. 435-438 (2002)