Diels - Alder反应合成3 -芳基化叶绿素- a衍生物及其消旋异构

IF 1.9 4区 化学 Q2 CHEMISTRY, ORGANIC Journal of Physical Organic Chemistry Pub Date : 2023-05-18 DOI:10.1002/poc.4546
Saki Kichishima, Hiroaki Maeda, Hitoshi Tamiaki
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引用次数: 0

摘要

以3-(反式-1,3-丁二烯基)氯与丙酸甲酯进行Diels-Alder反应,得到1,4-环己二烯的连续二脱氢反应,得到3位上含有o/m-(甲氧基羰基)苯基的邻苯二甲酸甲酯。3-芳基化氯的主要产物是围绕C3-C31键的高效液相色谱可分离旋转异构体的1:1混合物,而具有m-COOMe的次产物在室温下具有较小的空间阻碍,表现出快速的反异构化。主产物的3-芳基几乎垂直于氯π体系,与氯部分共轭较少,而次产物的π共轭较多,Qy谱带略有红移。虽然二氯甲烷中o-取代物的两种对映异构体具有相似的可见光吸收带和荧光发射数据,但它们在紫外- c光区的圆二色带依赖于立体化学。
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Synthesis of 3-arylated chlorophyll-a derivatives via Diels–Alder reaction and their atropisomerism

Methyl pyropheophorbides-a possessing an o/m-(methoxycarbonyl)phenyl group at the 3-position were prepared by Diels–Alder reaction of 3-(trans-1,3-butadienyl)chlorin with methyl propiolate and successive didehydrogenation of the resulting 1,4-cyclohexadienes. The 3-arylated chlorin bearing the sterically demanding o-COOMe group as the major product was a 1:1 mixture of high-performance liquid chromatography-separable rotational isomers around the C3–C31 bond, while the minor product with the m-COOMe was less sterically hindered to exhibit rapid atropisomerization at room temperature. The 3-aryl group of the major product was nearly perpendicular to the chlorin π-system and less conjugated with the chlorin moiety than that of the minor product wherein more π-conjugation occurred to give slightly red-shifted Qy bands. Although both the atropisomers of the o-substitute in dichloromethane showed similar visible absorption bands and fluorescence emission data, their circular dichroism bands in the ultraviolet-C light region were dependent on the stereochemistry.

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来源期刊
CiteScore
3.60
自引率
11.10%
发文量
161
审稿时长
2.3 months
期刊介绍: The Journal of Physical Organic Chemistry is the foremost international journal devoted to the relationship between molecular structure and chemical reactivity in organic systems. It publishes Research Articles, Reviews and Mini Reviews based on research striving to understand the principles governing chemical structures in relation to activity and transformation with physical and mathematical rigor, using results derived from experimental and computational methods. Physical Organic Chemistry is a central and fundamental field with multiple applications in fields such as molecular recognition, supramolecular chemistry, catalysis, photochemistry, biological and material sciences, nanotechnology and surface science.
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