Organic Synthesis Utilizing the Characteristic Properties of Hetero Atoms

利用杂原子特性的有机合成

• 批准号: 07405041
• 负责人: OGURA Katsuyuki
• 金额: $ 23.81万
• 依托单位: Chiba University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (A)
• 财政年份: 1995
• 资助国家: 日本
• 起止时间: 1995 至 1997
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-07405041/
• 关键词: Sulfur Atom; Nitrogen Atom; Fluorine Atom; Radical Asymmetric Induction; Benzene Ring Formation; alpha-Amino Acid; Functional Materials; Organometallic Macromolecules; ヘテロ原子; αーアミノ酸; ペルフルオロエチリデン; ジペプチド; ベンゼン環; 1,2-不斉誘起ラジカル反応; ベンゼン環形成反応; α-ア

We have investigated organic synthesis utilizing the characteristic properties of such hetero atoms as sulfur, nitrogen, and fluorine atoms to obtain the following fruitful results.i) Efficient 1,2-asymmetric induction in a radical addition : 1-Hydroxyalkyl radicals were found to add to gamma-hydroxy alpha-thio alpha, beta-unsaturated sulfones (or carboxylic esters) were revealed with extremely high efficiency. This is attributable to the conformational fixation around the beta, gamma-bond and the radical stabilization by a synergistic (captodative) effect of thio and sulfonyl (alkoxycarbonyl) groups.ii) Novel construction of a benzene ring : 1-methylthio (or chloro) -3- (p-tolylsulfonyl) -1,3,5-alkatrienes were found to thermally or photochemically give rise to benzene derivatives. We also found a novel construction of a benzene ring from a 1,3-alkadiene-5-yne.iii) Functional materials containing nitrogen and sulfur atoms : 1-Aryl-2,5di (2-thienyl) pyrroles, a new type of pi-electron … More systems, were shown to make it possible to develop efficient third-order nonlinear optics and EL-devices.iv) New synthesis of perfluoroethylidene-containing compounds : We found that a perfluoropropene-diethylamine adduct (PPDA) reacts with various allyl alcohols to form alpha-fluoro-alpha-trifluoromethyl-gamma-lactones and alpha-fluoro-alpha-trifluoromethyl-gamma, delta-unsaturated amides which are useful synthetic intermediates of many kinds of perfluoroethylidene-containing compounds.v) Self-assembly of macromolecules using reversible pyridine-palladium coordination bonds : Di-or tri (4-pyridyl) -containing ligands were found to react (en) Pd (NO3) 2 (en=ethylene diamine) in a selfassmbly manner to produce macromolecules such catenanes and three-dimensional cage-type compounds.vi) Molecular recognition in dipeptide crystals : (R) -Arylglycyl- (R) -phenylglycines (aryl=phenyl or 1-naphthyl) form inclusion crystals with various guest molecules. In the crystal, dipeptide molecules construct sheet structures and the guest molecules are accommodated between the sheets by means of hydrogen bonding, CH-pi interaction, and phenyl-phenyl edge-to-face interaction. Less

我们研究了利用硫、氮、氟等杂原子的特性进行有机合成，得到了以下丰硕的成果。i)有效的1,2-不对称诱导自由基加成：发现1-羟基烷基自由基以极高的效率加入-羟基α -硫- α， β -不饱和砜（或羧酸酯）。这是由于在β、γ键周围的构象固定以及硫和磺酰基（烷氧羰基）基团的协同（俘获）效应对自由基的稳定。ii)苯环的新结构：1-甲基硫（或氯）-3-（对甲基磺酰基）-1,3,5-烷三烯被发现可以通过热化学或光化学方法生成苯衍生物。我们还发现了一个由1,3-烷二烯-5-炔组成的苯环的新结构。iii)含氮和硫原子的功能材料：1-芳基-2,5二（2-噻基）吡咯，一种新型pi电子…更多的系统，使开发高效的三阶非线性光学和el器件成为可能。四)含全氟乙基化合物的新合成：我们发现全氟丙烯-二乙胺加合物（PPDA）与各种烯丙醇反应生成-氟- -三氟甲基- γ -内酯和-氟- -三氟甲基- γ - δ不饱和酰胺，它们是多种含全氟乙基化合物的有用合成中间体。v)利用可逆吡啶-钯配位键的大分子自组装：发现含二或三（4-吡啶基）的配体以自组装的方式反应（en） Pd (NO3) 2 （en=乙二胺），生成大分子，如连环烷和三维笼型化合物。六)二肽晶体中的分子识别：(R) -芳基甘氨酸- (R) -苯基甘氨酸（芳基=苯基或1-萘基）与各种客体分子形成包涵晶体。在晶体中，二肽分子构建薄片结构，客体分子通过氢键、CH-pi相互作用和苯基-苯基边对面相互作用被安置在薄片之间。少

项目成果

M.Fujita: "Catenane Formation from Two Molecular Rings through Very Rapid Slippage. A Mobius Strip Mechanism" J.Am.Chem.Soc.118. 899-900 (1996)

M.Fujita：“通过非常快速的滑移从两个分子环形成索烷。莫比乌斯带机制”J.Am.Chem.Soc.118。

M.Fujita: "Macrocyclic dinuclear complexes self-assembled from (en) Pd (NO_3) _2 and pyridine-based bridging ligands" Inorg.Chim.Acta. 246. 53-57 (1996)

M.Fujita：“由 (en) Pd (NO_3) _2 和基于吡啶的桥接配体自组装的大环双核配合物”Inorg.Chim.Acta。

M.Akazome: "Enantiomeric Recognition of Alkyl Phenyl Sulfoxides by Crystallin(R)-Phenylglycyl-(R)-phenylglycine" Tetrahedron. 53. 8315-8322 (1997)

M.Akazome：“Crystallin(R)-苯基甘氨酰-(R)-苯基甘氨酸对烷基苯基亚砜的对映体识别”四面体。

Hiroshi, Tomori: "Lipase-Catalyzed Practical Synthesis of(R)-1-Benzyl-3-hydroxy-2.5-pyrrolidinedione and Its Related Compounds" Bull.Chem.Soc.Jpn.69. 207-215 (1996)

Hiroshi, Tomori：“脂肪酶催化的(R)-1-苄基-3-羟基-2.5-吡咯烷二酮及其相关化合物的实际合成”Bull.Chem.Soc.Jpn.69。

Makoto, Fujita: "Macrocyclic dinuclear complexes self-assembled from(en)Pd(NO_3)_2 and pyridine-based bridging ligands" Inorg.Chim.Acta. 246. 53-57 (1996)

Makoto，Fujita：“由 (en)Pd(NO_3)_2 和基于吡啶的桥接配体自组装的大环双核配合物”Inorg.Chim.Acta。