Three-component diels-alder reaction through palladium carbene migratory insertion enabled dearomative C(sp3)-H bond activation
Abstract Owning to the versatile nature in participation of Diels-Alder (D-A) reactions, the development of efficient approaches to generate active ortho-quinodimethanes (o-QDMs) has gained much attention. However, a catalytic method involving coupling of two readily accessible components to constru...
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Nature Portfolio
2024-12-01
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| Series: | Nature Communications |
| Online Access: | https://doi.org/10.1038/s41467-024-55190-1 |
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| author | Yiman Mi Shuoyue Liu Lingfei Hu Yihua Wang Renhui Luo Yinghua Yu Zhiyang Zhang Shan Yuan Gang Lu Xueliang Huang |
| author_facet | Yiman Mi Shuoyue Liu Lingfei Hu Yihua Wang Renhui Luo Yinghua Yu Zhiyang Zhang Shan Yuan Gang Lu Xueliang Huang |
| author_sort | Yiman Mi |
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| description | Abstract Owning to the versatile nature in participation of Diels-Alder (D-A) reactions, the development of efficient approaches to generate active ortho-quinodimethanes (o-QDMs) has gained much attention. However, a catalytic method involving coupling of two readily accessible components to construct o-QDMs is lacking. Herein, we describe a palladium carbene migratory insertion enabled dearomative C(sp3)-H activation to form active o-QDM species through the cross-coupling of N-tosylhydrazones with aryl halides. The in situ generated o-QDM intermediates were trapped efficiently by 3-nitroindoles and N-sulfonylaldimines to provide dihydroindolo[2,3-b]carbazole derivatives and indole alkaloids modularly. To our knowledge, this reaction represents a rare example on three-component D-A cycloaddition through in situ generation of conjugated dienes by the coupling two readily available materials. We anticipate such a reaction mode could find broad application on diversity oriented six-membered ring construction. Deuterium labeling experiments and density functional theory calculations support a pathway through reversible C(sp3)-H activation to generate heterocyclic o-QDMs. |
| format | Article |
| id | doaj-art-441f3030fdba475d96e4cc21f9cf8c7c |
| institution | Kabale University |
| issn | 2041-1723 |
| language | English |
| publishDate | 2024-12-01 |
| publisher | Nature Portfolio |
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| series | Nature Communications |
| spelling | doaj-art-441f3030fdba475d96e4cc21f9cf8c7c2025-01-05T12:34:55ZengNature PortfolioNature Communications2041-17232024-12-0115111310.1038/s41467-024-55190-1Three-component diels-alder reaction through palladium carbene migratory insertion enabled dearomative C(sp3)-H bond activationYiman Mi0Shuoyue Liu1Lingfei Hu2Yihua Wang3Renhui Luo4Yinghua Yu5Zhiyang Zhang6Shan Yuan7Gang Lu8Xueliang Huang9Key Laboratory of Chemical Biology and Traditional Chinese Medicine Research, Ministry of Education of China, Key Laboratory of the Assembly and Application of Organic Functional Molecules of Hunan Province, College of Chemistry and Chemical Engineering, Hunan Normal UniversityKey Laboratory of Chemical Biology and Traditional Chinese Medicine Research, Ministry of Education of China, Key Laboratory of the Assembly and Application of Organic Functional Molecules of Hunan Province, College of Chemistry and Chemical Engineering, Hunan Normal UniversitySchool of Chemistry and Chemical Engineering, Key Laboratory of Colloid and Interface Chemistry, Ministry of Education, Shandong UniversityKey Laboratory of Chemical Biology and Traditional Chinese Medicine Research, Ministry of Education of China, Key Laboratory of the Assembly and Application of Organic Functional Molecules of Hunan Province, College of Chemistry and Chemical Engineering, Hunan Normal UniversityKey Laboratory of Chemical Biology and Traditional Chinese Medicine Research, Ministry of Education of China, Key Laboratory of the Assembly and Application of Organic Functional Molecules of Hunan Province, College of Chemistry and Chemical Engineering, Hunan Normal UniversityState Key Laboratory of Structure Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of SciencesKey Laboratory of Chemical Biology and Traditional Chinese Medicine Research, Ministry of Education of China, Key Laboratory of the Assembly and Application of Organic Functional Molecules of Hunan Province, College of Chemistry and Chemical Engineering, Hunan Normal UniversityKey Laboratory of Chemical Biology and Traditional Chinese Medicine Research, Ministry of Education of China, Key Laboratory of the Assembly and Application of Organic Functional Molecules of Hunan Province, College of Chemistry and Chemical Engineering, Hunan Normal UniversitySchool of Chemistry and Chemical Engineering, Key Laboratory of Colloid and Interface Chemistry, Ministry of Education, Shandong UniversityKey Laboratory of Chemical Biology and Traditional Chinese Medicine Research, Ministry of Education of China, Key Laboratory of the Assembly and Application of Organic Functional Molecules of Hunan Province, College of Chemistry and Chemical Engineering, Hunan Normal UniversityAbstract Owning to the versatile nature in participation of Diels-Alder (D-A) reactions, the development of efficient approaches to generate active ortho-quinodimethanes (o-QDMs) has gained much attention. However, a catalytic method involving coupling of two readily accessible components to construct o-QDMs is lacking. Herein, we describe a palladium carbene migratory insertion enabled dearomative C(sp3)-H activation to form active o-QDM species through the cross-coupling of N-tosylhydrazones with aryl halides. The in situ generated o-QDM intermediates were trapped efficiently by 3-nitroindoles and N-sulfonylaldimines to provide dihydroindolo[2,3-b]carbazole derivatives and indole alkaloids modularly. To our knowledge, this reaction represents a rare example on three-component D-A cycloaddition through in situ generation of conjugated dienes by the coupling two readily available materials. We anticipate such a reaction mode could find broad application on diversity oriented six-membered ring construction. Deuterium labeling experiments and density functional theory calculations support a pathway through reversible C(sp3)-H activation to generate heterocyclic o-QDMs.https://doi.org/10.1038/s41467-024-55190-1 |
| spellingShingle | Yiman Mi Shuoyue Liu Lingfei Hu Yihua Wang Renhui Luo Yinghua Yu Zhiyang Zhang Shan Yuan Gang Lu Xueliang Huang Three-component diels-alder reaction through palladium carbene migratory insertion enabled dearomative C(sp3)-H bond activation Nature Communications |
| title | Three-component diels-alder reaction through palladium carbene migratory insertion enabled dearomative C(sp3)-H bond activation |
| title_full | Three-component diels-alder reaction through palladium carbene migratory insertion enabled dearomative C(sp3)-H bond activation |
| title_fullStr | Three-component diels-alder reaction through palladium carbene migratory insertion enabled dearomative C(sp3)-H bond activation |
| title_full_unstemmed | Three-component diels-alder reaction through palladium carbene migratory insertion enabled dearomative C(sp3)-H bond activation |
| title_short | Three-component diels-alder reaction through palladium carbene migratory insertion enabled dearomative C(sp3)-H bond activation |
| title_sort | three component diels alder reaction through palladium carbene migratory insertion enabled dearomative c sp3 h bond activation |
| url | https://doi.org/10.1038/s41467-024-55190-1 |
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