Organocatalytic hydrogen bond donor/Lewis base (HBD/LB) synthesis and chiroptical properties of thiabridged [5]helicenes†

IF 2.7 3区化学 Q1 CHEMISTRY, ORGANIC

Organic & Biomolecular Chemistry Pub Date : 2024-09-11 DOI:10.1039/d4ob00979g

Michela Lupi , Mosè Fabbri , Giuseppe Mazzeo , Giovanna Longhi , Sergio Abbate , Caterina Viglianisi , Stefano Menichetti

引用次数: 0

Abstract

Thiabridged [5]helicenes are obtained from thioaryl-N-phthalimido benzo[a]phenothiazines using a hydrogen bond donor/Lewis base organocatalytic approach. Resolution of [5]helicenes using either (1S)-(−)-camphanic acid as a chiral auxiliary or CSP-HPLC is reported. Thiabridged [5]helicenes show an exceptional configurational stability with racemization energy barriers higher than 40 kcal mol⁻¹. Electronic circular dichroism and TD-DFT calculations permit the assignment of the absolute configuration, demonstrating that the sign of optical rotation is not easily related to the M or P structure. Separated enantiomers show circularly polarized luminescence with high dissymmetry ratio.

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有机催化氢键供体/刘易斯碱（HBD/LB）合成及硫杂[5]螺旋烯的光电性质。

利用氢键供体/刘易斯碱有机催化法，从硫代芳基-N-邻苯二甲酰亚胺基苯并[a]吩噻嗪中获得了硫杂[5]庚烯。报告采用 (1S)-(-)-莰烷酸作为手性辅助剂或 CSP-HPLC 法解析了 [5]helicenes。硫杂[5]螺旋烯显示出优异的构型稳定性，外消旋化能垒高于 40 kcal mol-1。通过电子圆二色性和 TD-DFT 计算，可以确定绝对构型，证明光学旋转的符号与 M 或 P 结构的关系并不简单。分离的对映体显示出高不对称率的圆偏振发光。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

Organic & Biomolecular Chemistry 化学-有机化学

CiteScore

5.50

自引率

9.40%

发文量

1056

审稿时长

1.3 months

期刊介绍： Organic & Biomolecular Chemistry is an international journal using integrated research in chemistry-organic chemistry. Founded in 2003 by the Royal Society of Chemistry, the journal is published in Semimonthly issues and has been indexed by SCIE, a leading international database. The journal focuses on the key research and cutting-edge progress in the field of chemistry-organic chemistry, publishes and reports the research results in this field in a timely manner, and is committed to becoming a window and platform for rapid academic exchanges among peers in this field. The journal's impact factor in 2023 is 2.9, and its CiteScore is 5.5.