利用机械化学反应† 完全无溶剂合成双杂环烯及其进一步的环融合

Honoka Sada, Daisuke Sakamaki, Masayuki Gon, Kazuo Tanaka, Takashi Hirose and Hideki Fujiwara
{"title":"利用机械化学反应† 完全无溶剂合成双杂环烯及其进一步的环融合","authors":"Honoka Sada, Daisuke Sakamaki, Masayuki Gon, Kazuo Tanaka, Takashi Hirose and Hideki Fujiwara","doi":"10.1039/D4MR00033A","DOIUrl":null,"url":null,"abstract":"<p >In this study, we developed a simple and efficient method for synthesizing double heterohelicenes (DHHs) composed of two heteroacenes bearing an NH group, such as benzo[<em>b</em>]phenoxazine (<strong>BPO</strong>) and dibenzo[<em>b</em>,<em>i</em>]phenoxazines (<strong>DBPO</strong>), using mechanochemical oxidative C–N coupling reactions, allowing complete solvent-free synthesis from commercially available compounds. Our new synthetic method afforded more than 1 g of DHH, which has a high dissymmetry factor for circularly polarized luminescence (<em>g</em><small><sub>CPL</sub></small>) of &gt;1 × 10<small><sup>−2</sup></small>, in a one-pot mechanochemical reaction using <strong>BPO</strong> as a reactant. In addition, mechanochemical oxidative coupling also allows for further fusion reactions of DHHs, leading to semi- or fully planarized molecules, which have not been previously achieved through solution-phase reactions. We isolated semi-planarized heterohelicenes <strong>5</strong> and <strong>6</strong> and determined their structures using single-crystal X-ray analysis. Compounds <strong>5</strong> and <strong>6</strong> exhibited enhanced electron donor properties compared to DHHs <strong>3</strong> and <strong>4</strong>. The enantiomers of <strong>6</strong> exhibited clear CPL emissions with a |<em>g</em><small><sub>CPL</sub></small>| value of 2 × 10<small><sup>−3</sup></small>. The magnitudes of the transition magnetic dipole moment (TMDM) of <strong>5</strong> and <strong>6</strong> increased compared to those of <strong>3</strong> and <strong>4</strong>. Transition moment density analysis revealed that large TMDM densities appeared on the newly formed C–C bonds, providing a unique molecular design guideline for enhancing the magnitude of the TMDM without expanding the molecular structure.</p>","PeriodicalId":101140,"journal":{"name":"RSC Mechanochemistry","volume":null,"pages":null},"PeriodicalIF":0.0000,"publicationDate":"2024-05-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/mr/d4mr00033a?page=search","citationCount":"0","resultStr":"{\"title\":\"Completely solvent-free synthesis of double heterohelicenes and their further ring fusion using mechanochemical reaction†\",\"authors\":\"Honoka Sada, Daisuke Sakamaki, Masayuki Gon, Kazuo Tanaka, Takashi Hirose and Hideki Fujiwara\",\"doi\":\"10.1039/D4MR00033A\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >In this study, we developed a simple and efficient method for synthesizing double heterohelicenes (DHHs) composed of two heteroacenes bearing an NH group, such as benzo[<em>b</em>]phenoxazine (<strong>BPO</strong>) and dibenzo[<em>b</em>,<em>i</em>]phenoxazines (<strong>DBPO</strong>), using mechanochemical oxidative C–N coupling reactions, allowing complete solvent-free synthesis from commercially available compounds. Our new synthetic method afforded more than 1 g of DHH, which has a high dissymmetry factor for circularly polarized luminescence (<em>g</em><small><sub>CPL</sub></small>) of &gt;1 × 10<small><sup>−2</sup></small>, in a one-pot mechanochemical reaction using <strong>BPO</strong> as a reactant. In addition, mechanochemical oxidative coupling also allows for further fusion reactions of DHHs, leading to semi- or fully planarized molecules, which have not been previously achieved through solution-phase reactions. We isolated semi-planarized heterohelicenes <strong>5</strong> and <strong>6</strong> and determined their structures using single-crystal X-ray analysis. Compounds <strong>5</strong> and <strong>6</strong> exhibited enhanced electron donor properties compared to DHHs <strong>3</strong> and <strong>4</strong>. The enantiomers of <strong>6</strong> exhibited clear CPL emissions with a |<em>g</em><small><sub>CPL</sub></small>| value of 2 × 10<small><sup>−3</sup></small>. The magnitudes of the transition magnetic dipole moment (TMDM) of <strong>5</strong> and <strong>6</strong> increased compared to those of <strong>3</strong> and <strong>4</strong>. Transition moment density analysis revealed that large TMDM densities appeared on the newly formed C–C bonds, providing a unique molecular design guideline for enhancing the magnitude of the TMDM without expanding the molecular structure.</p>\",\"PeriodicalId\":101140,\"journal\":{\"name\":\"RSC Mechanochemistry\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":0.0000,\"publicationDate\":\"2024-05-07\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"https://pubs.rsc.org/en/content/articlepdf/2024/mr/d4mr00033a?page=search\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"RSC Mechanochemistry\",\"FirstCategoryId\":\"1085\",\"ListUrlMain\":\"https://pubs.rsc.org/en/content/articlelanding/2024/mr/d4mr00033a\",\"RegionNum\":0,\"RegionCategory\":null,\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"\",\"JCRName\":\"\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"RSC Mechanochemistry","FirstCategoryId":"1085","ListUrlMain":"https://pubs.rsc.org/en/content/articlelanding/2024/mr/d4mr00033a","RegionNum":0,"RegionCategory":null,"ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"","JCRName":"","Score":null,"Total":0}
引用次数: 0

摘要

在这项研究中,我们开发了一种简单高效的方法,利用机械化学氧化 C-N 偶联反应合成由苯并[b]吩噁嗪(BPO)和二苯并[b,i]吩噁嗪(DBPO)等含有一个 NH 基团的两个杂环烯组成的双杂环烯(DHHs),从而实现了从市售化合物的完全无溶剂合成。我们的新合成方法以 BPO 为反应物,通过一锅机械化学反应制备了超过 1 克的 DHH,其圆极化发光不对称系数(gCPL)高达 1 × 10-2。此外,机械化学氧化偶联还能使 DHHs 发生进一步的融合反应,从而产生半平面化或全平面化分子,这在以前的溶液相反应中是无法实现的。我们分离出了半平面化的杂环烯 5 和 6,并通过单晶 X 射线分析确定了它们的结构。与二氢杂环烯 3 和 4 相比,化合物 5 和 6 表现出更强的电子供体特性。6 的对映体显示出清晰的 CPL 发射,|gCPL|值为 2 × 10-3。与 3 和 4 相比,5 和 6 的过渡磁偶极矩 (TMDM) 的大小有所增加。过渡磁矩密度分析表明,大的 TMDM 密度出现在新形成的 C-C 键上,这为在不扩大分子结构的情况下提高 TMDM 的大小提供了独特的分子设计指南。
本文章由计算机程序翻译,如有差异,请以英文原文为准。

Completely solvent-free synthesis of double heterohelicenes and their further ring fusion using mechanochemical reaction†

Completely solvent-free synthesis of double heterohelicenes and their further ring fusion using mechanochemical reaction†

In this study, we developed a simple and efficient method for synthesizing double heterohelicenes (DHHs) composed of two heteroacenes bearing an NH group, such as benzo[b]phenoxazine (BPO) and dibenzo[b,i]phenoxazines (DBPO), using mechanochemical oxidative C–N coupling reactions, allowing complete solvent-free synthesis from commercially available compounds. Our new synthetic method afforded more than 1 g of DHH, which has a high dissymmetry factor for circularly polarized luminescence (gCPL) of >1 × 10−2, in a one-pot mechanochemical reaction using BPO as a reactant. In addition, mechanochemical oxidative coupling also allows for further fusion reactions of DHHs, leading to semi- or fully planarized molecules, which have not been previously achieved through solution-phase reactions. We isolated semi-planarized heterohelicenes 5 and 6 and determined their structures using single-crystal X-ray analysis. Compounds 5 and 6 exhibited enhanced electron donor properties compared to DHHs 3 and 4. The enantiomers of 6 exhibited clear CPL emissions with a |gCPL| value of 2 × 10−3. The magnitudes of the transition magnetic dipole moment (TMDM) of 5 and 6 increased compared to those of 3 and 4. Transition moment density analysis revealed that large TMDM densities appeared on the newly formed C–C bonds, providing a unique molecular design guideline for enhancing the magnitude of the TMDM without expanding the molecular structure.

求助全文
通过发布文献求助,成功后即可免费获取论文全文。 去求助
来源期刊
自引率
0.00%
发文量
0
×
引用
GB/T 7714-2015
复制
MLA
复制
APA
复制
导出至
BibTeX EndNote RefMan NoteFirst NoteExpress
×
提示
您的信息不完整,为了账户安全,请先补充。
现在去补充
×
提示
您因"违规操作"
具体请查看互助需知
我知道了
×
提示
确定
请完成安全验证×
copy
已复制链接
快去分享给好友吧!
我知道了
右上角分享
点击右上角分享
0
联系我们:info@booksci.cn Book学术提供免费学术资源搜索服务,方便国内外学者检索中英文文献。致力于提供最便捷和优质的服务体验。 Copyright © 2023 布克学术 All rights reserved.
京ICP备2023020795号-1
ghs 京公网安备 11010802042870号
Book学术文献互助
Book学术文献互助群
群 号:481959085
Book学术官方微信