基于分子内的仿生Diels-Alder反应构建Elansolid A1/A2的四氢茚烷核心结构

doi:10.6023/cjoc202102021

有机化学 ›› 2021, Vol. 41 ›› Issue (7): 2820-2830.DOI: 10.6023/cjoc202102021 上一篇下一篇

研究论文

基于分子内的仿生Diels-Alder反应构建Elansolid A1/A2的四氢茚烷核心结构

于奇^a, 杨帅^b, 唐聪云^a, 彭林^a^,^*(), 左之利^b^,^*(), 汪亮亮^b^,^*()

a 邵阳学院食品与化学工程学院湖南邵阳 422000
b 中国科学院昆明植物研究所昆明 650201

收稿日期:2021-02-06 修回日期:2021-03-30 发布日期:2021-04-06
通讯作者: 彭林, 左之利, 汪亮亮
基金资助:
中国科学院“西部之光”; 中国科学院青年创新促进会; 国家自然科学基金(21772207); 云南省千人计划; 湖南省教育厅(19c1655)

Biomimetic Intramolecular Diels-Alder Reaction to Construct the Tetrahydroindane Core of Elansolid A1/A2

Qi Yu^a, Shuai Yang^b, Congyun Tang^a, Lin Peng^a(), Zhili Zuo^b(), Liangliang Wang^b()

a School of Food and Chemical Engineering, Shaoyang University, Shaoyang, Hunan 422000
b State Key Laboratory of Phytochemistry and Plant Resources in West China, Kunming Institute of Botany, Chinese Academy of Sciences, Kunming, 650201

Received:2021-02-06 Revised:2021-03-30 Published:2021-04-06
Contact: Lin Peng, Zhili Zuo, Liangliang Wang
Supported by:
“Light of West China” Program; Youth Innovation Promotion Association of the Chinese Academy of Sciences; National Natural Science Foundation of China(21772207); “Thousand Talents Program” of Yunnan Province; Program from Education Department of Hunan Province(19c1655)

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摘要/Abstract

Elansolid A1/A2是从滑行细菌Chitinophaga sanctii中分离出来的次级代谢产物, 具有抗菌活性. 迄今为止, 该天然产物的全合成尚未被报道, 主要由于其化学结构复杂, 包含反式四氢茚烷单元、(Z)-(E)-(Z)共轭三烯及19元大环内酯结构. 在此研究中, 两种含氧官能团的底物被合成出来并考察了这两种底物在手性磷酸催化下进行分子内的仿生Diels-Alder反应(IMDA), 成功地构建了Elansolid A1/A2中的反式四氢茚烷核心骨架, 且该Diels-Alder反应的非对映选择性提高到了1.8∶1以及减少了合成步骤.

关键词: 仿生合成, Diels-Alder反应, 四氢茚烷, Elansolid

The Elansolid A1/A2 is metabolite from the gliding bacteriumChitinophaga sanctiiand shows antibiotic activity against Gram-positive bacteria. Up to now, the total synthesis of this natural product has not been reported yet due to its structure complexity, which arises from thetrans-tetrahydroindane unit and (Z)-(E)-(Z) triene motif as well as a 19-member macrolactone. In this study, two newO-functionalized substrates were synthesized to undergo the biomimetic intramolecular Diels-Alder reactions (IMDA) catalyzed by a chiral phosphoric acid to build the keytrans-tetrahydroindane core of Elansolid A1/A2 via a vinylicp-quinone methide intermediate. This result shows that an improveddr (1.8∶1) of IMDA reaction and shorter synthetic steps could be achieved.

Key words: biomimetic synthesis, Diels-Alder reaction, tetrahydroindane, elansolid

引用此文

于奇, 杨帅, 唐聪云, 彭林, 左之利, 汪亮亮. 基于分子内的仿生Diels-Alder反应构建Elansolid A1/A2的四氢茚烷核心结构[J]. 有机化学, 2021, 41(7): 2820-2830.

Qi Yu, Shuai Yang, Congyun Tang, Lin Peng, Zhili Zuo, Liangliang Wang. Biomimetic Intramolecular Diels-Alder Reaction to Construct the Tetrahydroindane Core of Elansolid A1/A2[J]. Chinese Journal of Organic Chemistry, 2021, 41(7): 2820-2830.

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图/表 6

Figure 1. Elansolids natural products

Scheme 1. Reported biomimetic IMDA reaction and Lewis acid IMDA reaction respectively applied in the total synthesis of 20-deoxyl- Elansolid B1 and Elansolid B1

Figure 2. Devised O-functionalized IMDA substrates 1 and 2

Scheme 2. Synthesis of precursor 1 and biomimetic IMDA reaction DIPEA (diisopropylethylamine), DMP (dess-martin periodinane), NaHMDS (sodium bis(trimethylsilyl)amide), TBS, TMS (trimethylsilyl), TBAF, TBDPS (t-butyldiphenylsilyl), CPA (chiral phosphoric acid)

Scheme 3. Synthesis of precursor 2 and biomimetic IMDA reaction. LiHMDS (Lithium bis(trimethylsilyl)amide)

Scheme 4. Determination of the relative configuration of “Evans anti-aldol” product 6. DIBAL-H (diisobutylaluminum hydride), D-(+)-CSA (camphorsufonic acid)

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基于分子内的仿生Diels-Alder反应构建Elansolid A1/A2的四氢茚烷核心结构

Biomimetic Intramolecular Diels-Alder Reaction to Construct the Tetrahydroindane Core of Elansolid A1/A2

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