Asymmetric Synthesis of Dialkyl Carbinols by Ni‐Catalyzed Reductive‐Oxidative Relay of Distinct Alkenes
Abstract Enantioenriched unsymmetric dialkyl carbinol derivatives are of importance in natural products, bioactive molecules, and functional organic materials. However, the catalytic asymmetric synthesis of dialkyl carbinol derivatives remains challenging due to the similar steric and electronic pro...
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Wiley
2024-12-01
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| Series: | Advanced Science |
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| Online Access: | https://doi.org/10.1002/advs.202409592 |
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| author | Quan‐Xing Zi Wei Shu |
| author_facet | Quan‐Xing Zi Wei Shu |
| author_sort | Quan‐Xing Zi |
| collection | DOAJ |
| description | Abstract Enantioenriched unsymmetric dialkyl carbinol derivatives are of importance in natural products, bioactive molecules, and functional organic materials. However, the catalytic asymmetric synthesis of dialkyl carbinol derivatives remains challenging due to the similar steric and electronic properties of two alkyl substituents. Herein, an unprecedented synthesis of chiral dialkyl carbinol ester derivatives from Ni‐catalyzed reductive‐oxidative relay cross‐coupling of two alkenes is developed for the first time. The reaction features the use of enol esters and unactivated alkenes as two different alkyl equivalents to undergo head‐to‐tail and enantioselective alkyl‐alkyl cross‐coupling. The reaction undergoes two‐electron reduction and single electron oxidation in the presence of both reductants and oxidants. The use of an allyl bromide as single electron acceptor is crucial for the success of this non‐trivial asymmetric cross‐coupling, providing a new reaction mode for asymmetric alkyl‐alkyl bond‐forming event in the absence of stoichiometric alkyl electrophiles. |
| format | Article |
| id | doaj-art-ee490fb4cacd490cbcf52442bc8e576e |
| institution | OA Journals |
| issn | 2198-3844 |
| language | English |
| publishDate | 2024-12-01 |
| publisher | Wiley |
| record_format | Article |
| series | Advanced Science |
| spelling | doaj-art-ee490fb4cacd490cbcf52442bc8e576e2025-08-20T02:01:00ZengWileyAdvanced Science2198-38442024-12-011148n/an/a10.1002/advs.202409592Asymmetric Synthesis of Dialkyl Carbinols by Ni‐Catalyzed Reductive‐Oxidative Relay of Distinct AlkenesQuan‐Xing Zi0Wei Shu1Guangming Advanced Research Institute Department of Chemistry and Guangdong Provincial Key Laboratory of Catalysis Southern University of Science and Technology Shenzhen Grubbs Institute Shenzhen Guangdong 518055 P. R. ChinaGuangming Advanced Research Institute Department of Chemistry and Guangdong Provincial Key Laboratory of Catalysis Southern University of Science and Technology Shenzhen Grubbs Institute Shenzhen Guangdong 518055 P. R. ChinaAbstract Enantioenriched unsymmetric dialkyl carbinol derivatives are of importance in natural products, bioactive molecules, and functional organic materials. However, the catalytic asymmetric synthesis of dialkyl carbinol derivatives remains challenging due to the similar steric and electronic properties of two alkyl substituents. Herein, an unprecedented synthesis of chiral dialkyl carbinol ester derivatives from Ni‐catalyzed reductive‐oxidative relay cross‐coupling of two alkenes is developed for the first time. The reaction features the use of enol esters and unactivated alkenes as two different alkyl equivalents to undergo head‐to‐tail and enantioselective alkyl‐alkyl cross‐coupling. The reaction undergoes two‐electron reduction and single electron oxidation in the presence of both reductants and oxidants. The use of an allyl bromide as single electron acceptor is crucial for the success of this non‐trivial asymmetric cross‐coupling, providing a new reaction mode for asymmetric alkyl‐alkyl bond‐forming event in the absence of stoichiometric alkyl electrophiles.https://doi.org/10.1002/advs.202409592alkene‐alkene couplingasymmetric alkyl‐alkyl couplingdialkyl carbinolsnickel catalysisreductive‐oxidative relay |
| spellingShingle | Quan‐Xing Zi Wei Shu Asymmetric Synthesis of Dialkyl Carbinols by Ni‐Catalyzed Reductive‐Oxidative Relay of Distinct Alkenes Advanced Science alkene‐alkene coupling asymmetric alkyl‐alkyl coupling dialkyl carbinols nickel catalysis reductive‐oxidative relay |
| title | Asymmetric Synthesis of Dialkyl Carbinols by Ni‐Catalyzed Reductive‐Oxidative Relay of Distinct Alkenes |
| title_full | Asymmetric Synthesis of Dialkyl Carbinols by Ni‐Catalyzed Reductive‐Oxidative Relay of Distinct Alkenes |
| title_fullStr | Asymmetric Synthesis of Dialkyl Carbinols by Ni‐Catalyzed Reductive‐Oxidative Relay of Distinct Alkenes |
| title_full_unstemmed | Asymmetric Synthesis of Dialkyl Carbinols by Ni‐Catalyzed Reductive‐Oxidative Relay of Distinct Alkenes |
| title_short | Asymmetric Synthesis of Dialkyl Carbinols by Ni‐Catalyzed Reductive‐Oxidative Relay of Distinct Alkenes |
| title_sort | asymmetric synthesis of dialkyl carbinols by ni catalyzed reductive oxidative relay of distinct alkenes |
| topic | alkene‐alkene coupling asymmetric alkyl‐alkyl coupling dialkyl carbinols nickel catalysis reductive‐oxidative relay |
| url | https://doi.org/10.1002/advs.202409592 |
| work_keys_str_mv | AT quanxingzi asymmetricsynthesisofdialkylcarbinolsbynicatalyzedreductiveoxidativerelayofdistinctalkenes AT weishu asymmetricsynthesisofdialkylcarbinolsbynicatalyzedreductiveoxidativerelayofdistinctalkenes |