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|a 10.1002/jcc.27277
|2 doi
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|a eng
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| 100 |
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|a Bai, Yuna
|e verfasserin
|4 aut
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|a Mechanistic study of the Ni-catalyzed hydroalkylation of 1,3-dienes
|b The origins of regio- and enantioselectivities and a further rational design
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|c 2024
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|a Text
|b txt
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|a ƒaComputermedien
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|a ƒa Online-Ressource
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|a Date Revised 01.03.2024
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|a published: Print-Electronic
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|a Citation Status PubMed-not-MEDLINE
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|a © 2023 Wiley Periodicals LLC.
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|a The development of the catalytic regio- and enantioselective hydrofunctionalization of 1,3-dienes remains a challenge and requires deep insight into the reaction mechanisms. We herein thoroughly studied the reaction mechanism of the Ni-catalyzed hydroalkylation of 1,3-dienes with ketones by density functional theory (DFT) calculations. It reveals that the reaction is initiated by stepwise oxidative addition of EtO-H followed by 1,3-diene migratory insertion to generate the alkylnickel(II) intermediate, rather than the experimentally proposed ligand-to-ligand hydrogen transfer (LLHT) mechanism. In addition, we rationalized the role of t BuOK in the subsequent addition of enolate of ketone and transmetalation process. Based on the whole catalysis, the CC reductive elimination step, turns out to be the rate- and enantioselectivity-determining step. Furthermore, we disclosed the origins of the regio- and enantioselectivity of the product, and found that the 1,2-selectivity lies in the combination effects of the ligand-substrate electrostatic interactions, orbital interactions and Pauli repulsions, while the enantioselectivity mainly arises from substrate-ligand steric repulsions. Based on mechanistic study, new biaryl bisphosphine ligands affording higher enantioselectivity were designed, which will help to improve current catalytic systems and develop new transition-metal-catalyzed hydroalkylations
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|a Journal Article
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|a enantioselectivity
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| 650 |
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4 |
|a hydroalkylation
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| 650 |
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4 |
|a ligand design
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| 650 |
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4 |
|a reaction mechanism
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| 650 |
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4 |
|a regioselectivity
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| 700 |
1 |
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|a Xian, Anmei
|e verfasserin
|4 aut
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| 700 |
1 |
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|a Yang, Xing
|e verfasserin
|4 aut
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| 700 |
1 |
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|a Zhou, Ming
|e verfasserin
|4 aut
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| 700 |
1 |
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|a Zhao, Xuefei
|e verfasserin
|4 aut
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| 700 |
1 |
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|a Zhao, Lili
|e verfasserin
|4 aut
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| 773 |
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|i Enthalten in
|t Journal of computational chemistry
|d 1984
|g 45(2024), 10 vom: 15. März, Seite 610-621
|w (DE-627)NLM098138448
|x 1096-987X
|7 nnns
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| 773 |
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|g volume:45
|g year:2024
|g number:10
|g day:15
|g month:03
|g pages:610-621
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|u http://dx.doi.org/10.1002/jcc.27277
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