Anti-Markovnikov hydroallylation reaction of alkenes via scandium-catalyzed allylic C‒H activation
Abstract Compared with rare-earth (RE)…heteroatom interaction, RE…π interaction, frequently used in facilitating regio- and stereoselectivity of olefin polymerizations, is seldomly used to trigger catalytic C − H functionalization. Here, we describe a direct anti-Markovnikov hydroallylation reaction...
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| Format: | Article |
| Language: | English |
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Nature Portfolio
2025-02-01
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| Series: | Nature Communications |
| Online Access: | https://doi.org/10.1038/s41467-025-56602-6 |
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| author | Shiyu Wang Lichao Ning Tao Mao Yuqiao Zhou Maoping Pu Xiaoming Feng Shunxi Dong |
| author_facet | Shiyu Wang Lichao Ning Tao Mao Yuqiao Zhou Maoping Pu Xiaoming Feng Shunxi Dong |
| author_sort | Shiyu Wang |
| collection | DOAJ |
| description | Abstract Compared with rare-earth (RE)…heteroatom interaction, RE…π interaction, frequently used in facilitating regio- and stereoselectivity of olefin polymerizations, is seldomly used to trigger catalytic C − H functionalization. Here, we describe a direct anti-Markovnikov hydroallylation reaction of styrene derivatives with 1-aryl-2-alkyl alkenes and α-alkenes by use of RE…π interaction. This protocol provides a straightforward and atom-efficient route for the synthesis of valuable chain elongated internal alkenes (65 examples, up to 99% yield, > 19:1 E/Z ratio). The reaction proceeds via an allylic Csp3‒H activation pathway initiated by site-selective deprotonation with the assistance of cationic imidazolin-2-iminato scandium alkyl species followed by alkene insertion into the resulting scandium-allyl bond. A catalytic amount of Lewis base additives, such as amine and tetrahydrofuran (THF) show significant effects on the reactivity and E/Z selectivity. The reaction mechanism is elucidated by experimental studies and theoretical calculations. |
| format | Article |
| id | doaj-art-f0071bb8db01479aba63d5a42a4f56da |
| institution | Kabale University |
| issn | 2041-1723 |
| language | English |
| publishDate | 2025-02-01 |
| publisher | Nature Portfolio |
| record_format | Article |
| series | Nature Communications |
| spelling | doaj-art-f0071bb8db01479aba63d5a42a4f56da2025-02-09T12:43:54ZengNature PortfolioNature Communications2041-17232025-02-0116111110.1038/s41467-025-56602-6Anti-Markovnikov hydroallylation reaction of alkenes via scandium-catalyzed allylic C‒H activationShiyu Wang0Lichao Ning1Tao Mao2Yuqiao Zhou3Maoping Pu4Xiaoming Feng5Shunxi Dong6Key Laboratory of Green Chemistry & Technology Ministry of Education, College of Chemistry Sichuan UniversityKey Laboratory of Green Chemistry & Technology Ministry of Education, College of Chemistry Sichuan UniversityKey Laboratory of Green Chemistry & Technology Ministry of Education, College of Chemistry Sichuan UniversityKey Laboratory of Green Chemistry & Technology Ministry of Education, College of Chemistry Sichuan UniversityKey Laboratory of Green Chemistry & Technology Ministry of Education, College of Chemistry Sichuan UniversityKey Laboratory of Green Chemistry & Technology Ministry of Education, College of Chemistry Sichuan UniversityKey Laboratory of Green Chemistry & Technology Ministry of Education, College of Chemistry Sichuan UniversityAbstract Compared with rare-earth (RE)…heteroatom interaction, RE…π interaction, frequently used in facilitating regio- and stereoselectivity of olefin polymerizations, is seldomly used to trigger catalytic C − H functionalization. Here, we describe a direct anti-Markovnikov hydroallylation reaction of styrene derivatives with 1-aryl-2-alkyl alkenes and α-alkenes by use of RE…π interaction. This protocol provides a straightforward and atom-efficient route for the synthesis of valuable chain elongated internal alkenes (65 examples, up to 99% yield, > 19:1 E/Z ratio). The reaction proceeds via an allylic Csp3‒H activation pathway initiated by site-selective deprotonation with the assistance of cationic imidazolin-2-iminato scandium alkyl species followed by alkene insertion into the resulting scandium-allyl bond. A catalytic amount of Lewis base additives, such as amine and tetrahydrofuran (THF) show significant effects on the reactivity and E/Z selectivity. The reaction mechanism is elucidated by experimental studies and theoretical calculations.https://doi.org/10.1038/s41467-025-56602-6 |
| spellingShingle | Shiyu Wang Lichao Ning Tao Mao Yuqiao Zhou Maoping Pu Xiaoming Feng Shunxi Dong Anti-Markovnikov hydroallylation reaction of alkenes via scandium-catalyzed allylic C‒H activation Nature Communications |
| title | Anti-Markovnikov hydroallylation reaction of alkenes via scandium-catalyzed allylic C‒H activation |
| title_full | Anti-Markovnikov hydroallylation reaction of alkenes via scandium-catalyzed allylic C‒H activation |
| title_fullStr | Anti-Markovnikov hydroallylation reaction of alkenes via scandium-catalyzed allylic C‒H activation |
| title_full_unstemmed | Anti-Markovnikov hydroallylation reaction of alkenes via scandium-catalyzed allylic C‒H activation |
| title_short | Anti-Markovnikov hydroallylation reaction of alkenes via scandium-catalyzed allylic C‒H activation |
| title_sort | anti markovnikov hydroallylation reaction of alkenes via scandium catalyzed allylic c h activation |
| url | https://doi.org/10.1038/s41467-025-56602-6 |
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