ABSOLUTE ASYMMETRIC SYNTHESIS IN HOMOGENEOUS CONDITIONS USING THE CHIRAL CRYSTALLINE ENVIRONMENT AND TOTAL RESOLUTION VIA PHOTORACEMIZATION-CRYSTALLIZATION

使用手性晶体环境在均相条件下进行绝对不对称合成并通过光乙酰化结晶获得总分辨率

• 批准号: 13640524
• 负责人: SAKAMOTO Masami
• 金额: $ 2.3万
• 依托单位: CHIBA UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 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/grant/KAKENHI-PROJECT-13640524/
• 关键词: CHIRAL CRYSTAL; TOPOCHEMICAL; PHOTOCHEMICAL REACTION; SOLID-STATE REACTION; ASYMMETRIC SYNTHESIS; ABSOLUTE ASYMMETIRC SYNTHESIS; CRYSTAL STRUCTURAL ANALYSIS; SPACE GROUP; 不斉結晶; 不斉合成; 光反応; コングロマレート

The achievement of an asymmetric synthesis starting from an achiral reagent and in the absence of any external chiral agent has long been an intriguing challenge to chemists and is also central to the problem of the origin of optically activity in nature. Stereospecific solid-state chemical reactions of chiral crystals formed by achiral materials are defined as "absolute" asymmetric synthesis. This symmetric synthesis involves new concept of absolute asymmetric synthesis using the frozen chirality memoried by chiral crystallization.We found that the stereo-controlled photochemical reaction could occur in the solid state. Furthermore, new absolute asymmetric synthesis in homogeneous conditions using chiral christals were also demonstrated. We found achiral acyclic imides with bulky substituents on the nitrogen atom crystallized in chiral space group, and maintain the chiral conformation when the crystals dissolved in THF at low-temperature. The reaction with n-butyllithium at a range of -80-20℃ gave optically active butyl adduct and hydrogenated product. This reaction provides the first example of absolute asymmetric synthesis using chiral crystals in homogeneous conditions.

从非手性试剂出发，在没有任何外部手性试剂的情况下实现不对称合成一直是化学家们感兴趣的挑战，也是自然界中光学活性起源问题的核心。由非手性物质形成手性晶体的立体定向固相化学反应被定义为“绝对”不对称合成。这种对称合成涉及到利用手性结晶记忆的冻结手性进行绝对不对称合成的新概念，我们发现立体控制的光化学反应可以在固态下进行。此外，还证明了在均相条件下使用手性化合物的新的绝对不对称合成。我们发现氮原子上有大取代基的非手性非环状酰亚胺以手性空间群结晶，低温下溶于THF中仍保持手性构象。与正丁基锂在-80-20℃反应，得到光学活性的丁基加成物和氢化产物。该反应提供了在均相条件下使用手性晶体进行绝对不对称合成的第一个实例。

项目成果

Masami Sakamoto: "Photocycloaddition reactions of alkyl and aryl 2-thioxo-3H-benzoxazole-3-carboxylates to alkenes"Helv.Chim.Acta.. 85・8. 2383-2393 (2002)

坂本正美：“2-硫代-3H-苯并恶唑-3-羧酸烷基酯和芳基酯与烯烃的光环加成反应”Helv.Chim.Acta.. 85・8（2002）。

Masami Sakamoto: "Palladium-catalyzed Asymmetric Allylic Alkylation using Chiral Prolinol-Drived Aminophophine Ligands"Heterocycles. 60. 9-13 (2003)

Masami Sakamoto：“使用手性脯氨醇驱动的氨基膦配体进行钯催化的不对称烯丙基烷基化”杂环。

Masami SAKAMOTO et al.: "Photochemistry of Thioamides and Thioimides, in CRC Handbook of Organic Photochemistry and Photobiology"CRC Press. (2003)

Masami SAKAMOTO 等人：“硫代酰胺和硫代酰亚胺的光化学，见 CRC 有机光化学和光生物学手册”CRC Press。

Masami Sakamoto: "Chiral Photochemistry"Absolute Asymmetric Photochemistry using Spontaneous Chiral Crystallization (In press). (2003)

Masami Sakamoto：“手性光化学”使用自发手性结晶的绝对不对称光化学（正在出版）。

Masami Sakamoto: "Diastereoselective Formation of Cage-type Adducts via A Novel Photoreaction of Nicotinic Acid Esters with Furan"Tetrahedron Lett.. 43. 6103-6105 (2002)

坂本正美：“通过烟酸酯与呋喃的新型光反应非对映选择性形成笼型加合物”Tetrahedron Lett.. 43. 6103-6105 (2002)