Synthesis of Functionalized Norcaradiene Derivatives

功能化去甲二烯衍生物的合成

• 批准号: 06640679
• 负责人: KOHMOTO Shigeo
• 金额: $ 1.34万
• 依托单位: CHIBA UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (C)
• 财政年份: 1994
• 资助国家: 日本
• 起止时间: 1994 至 1995
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-06640679/
• 关键词: Norcaradiene; Valence isomerization; Conformation control; Solvatochromic; Cyclopropene; Hydrogen transferred photorearrangement; Aromatization; 光[2+2]環化付加反応; コンフォメーション制御; バレンス異性化; 光[2+2]環化反応; スピロラクトン

Utilization of norcaradiene-cycloheptatriene valence isomerization, one of the most typical valence isomerization, was attempted for a development of new functinalized materials.(1) Attempt to develop a new solvatochromic system ; Control of norcaradiene-cycloheptatriene valence isomerization has been accomplished in 1,7-lactone and 1,7-lactam ring fused norcaradienes by protonation. Remarkable carbon chemical shift change was observed.(2) Conformational control of 1,7-lactol ring fused norcaradienes ; Using intramolecular hydrogen bonding, the restricted rotation occurring in the norcaradiene system was locked. This locking was unlocked by the solvation with alcohol or dimethyl sulfoxide.(3) Selective cleavage of cyclopropane sigma-bond of norcaradiene ; The C_1-C_7 bond of 1,7-lactol ring fused norcaradienes was selectively and conveniently cleaved to result in the dehydrative aromatization.(4) Mechanism of the hydrogen transferred photorearrangement ; In order to elucidate the mechanism of the hydrogen transferred photorearrangement often reported in the photo [2+2] cycloaddition, photochemistry of cyclopropene derivatives (synthetic intermediate for norcaradienes) was investigated. It was found that steric factors controlled the course of photoreaction whether a [2+2] cycloaddition or a hydrogen transferred rearrangement.

本文试图利用降冰片二烯-环庚三烯化合物的价态异构化反应来开发新的功能化材料。(1)尝试开发一种新的溶剂化显色体系;在1，7-内酯和1，7-内酰胺环稠合的降冰片二烯中，通过质子化实现了降冰片二烯-环庚三烯的价态异构化控制。观察到了显著的碳化学位移变化。(2)1，7-内半缩醛环稠合降冰片二烯的构象控制利用分子内氢键作用，将降冰片二烯体系中的受限旋转锁定。这种锁定通过用乙醇或二甲基亚砜溶剂化来解锁。(3)降冰片二烯环丙烷σ-键的选择性断裂1，7-内缩醛环稠合的降冰片二烯的C_1-C_7键被选择性、方便地断裂，导致脱水芳构化。(4)氢转移光重排反应机理：为了阐明光[2+2]环加成反应中氢转移光重排反应的机理，研究了环丙烯衍生物（降冰片二烯的合成中间体）的光化学反应。发现无论是[2+2]环加成反应还是氢转移重排反应，空间位阻因素都控制着反应的进程。

项目成果

Shigeo Kohmoto: "Conformation of acylureas. Solvent polarity dependent specific rotation and the formation of molecular complexes with solvent molecules" J. Chem. Soc., Perkin Trans. 2. (印刷中). (1996)

Shigeo Kohmoto：“酰基脲的构象。溶剂极性依赖性比旋光度和与溶剂分子形成分子复合物”J. Chem. Soc.，Perkin Trans 2.（出版中）。

Shigeo Kohmoto, Ichiro Koyano, Teruyuki Kawatsuji, Hideaki Kashimura, Keiki Kishikawa, Makoto Yamamoto, and Kazutoshi Yamada: "Conformation of 7-Vinylnorcaradienes. Conformational Locking by Intramolecular Hydrogen Bonding and Its Unlocking by Solvation."

Shigeo Kohmoto、Ichiro Koyano、Teruyuki Kawatsuji、Hideaki Kashimura、Keiki Kishikawa、Makoto Yamamoto 和 Kazutoshi Yamada：“7-Vinylnorcaradienes 的构象。分子内氢键的构象锁定及其通过溶剂化的解锁。”

Shigeo KHOMOTO: "Acid catalyzed dehydrative Aromatization of 1,7-lactol ring fused and 7-hydroxymethyl norcaradienes : A specific cleavage of the C_1-C_7 bond." Tetrahedron Lett.36. 553-554 (1995)

Shigeo KHOMOTO：“1,7-乳醇环稠合和 7-羟甲基去甲二烯的酸催化脱水芳构化：C_1-C_7 键的特异性断裂。”

Keiki Kishikawa: "Novel Three-Component Couping Reaction of Carbodiimide,Methyl Hydrogen Maleate,and an Alcohol or Aimine:Synthesis of N-Carbamoylaspartic Acid." Journal of Chemical Society,Perkin Trans.1. 1205-1209 (1994)

Keiki Kishikawa：“碳二亚胺、马来酸甲酯和醇或胺的新型三组分偶联反应：N-氨基甲酰天冬氨酸的合成”。

Shigeo KOHMOTO: "Photochemical formal [4π+2π+2π] cycloreversion of 7,8-diaza-3-oxatricyclo [4.2.1.0^<2,5>] non-7-enes." J.Phys.Org.Chem.8. 899-904 (1995)

Shigeo KOHMOTO：“7,8-二氮杂-3-氧杂三环 [4.2.1.0^<2,5>] 非 7-烯的光化学形式 [4π+2π+2π] 环化回复。”J.Phys.Org.Chem。 8.899-904 (1995)