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.

本研究的目的是建立以液晶为介质的高度定向调控反应体系的新方法，该体系具有规律性和流动性。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（单分子反应）：反式-4-环己基环己基十碳三烯酸酯在近晶液晶溶剂如双(4-戊氧基苯基)反式-1,4-环己烷二甲酸酯 (BPCD)研究发现，双环环加合物具有极高的非对映选择性和化学产率，而各向同性介质如 4-戊氧基苯基环己烷甲酸酯 (PCC) 和均三甲苯的结果较差。(2)分子间 [4+2] 环加成（双分子反应）：中等观察吡咯和丙二烯分子间环加成的立体选择性和反应加速效应(3)光延反应（四分子反应）：在近晶介质中观察到反式4-取代环己醇的羟基构型通过光延反应异常保留，这与通常的结果（构型反转）相反。各向同性介质。

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)

T.Katahira, T.Ishizuka, H.Matsunaga, T.Kunieda: "Stereoselective intramolecular radical addition of polyhaloacyl pendant groups to the 1,3-dihydro-2-imidazolone moiety : the chiral synthesis of treo-diaminocarboxyliv acids"Tetrahedron Letters. 42. 6319-63

T.Katahira、T.Ishizuka、H.Matsunaga、T.Kunieda：“多卤酰基侧基与 1,3-二氢-2-咪唑啉酮部分的立体选择性分子内自由基加成：三二氨基羧基酸的手性合成”四面体快报。