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Palladium-catalyzed cross-coupling of alcohols with olefins by positional tuning of a counteranion.

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Title: Palladium-catalyzed cross-coupling of alcohols with olefins by positional tuning of a counteranion.
Authors: Kaster, Sven H. M., Lei Zhu, Lyon, William L., Rulin Ma, Ammann, Stephen E., White, M. Christina
Source: Science (pre-March 2025). 9/6/2024, Vol. 385 Issue 6713, p1067-1076. 10p. 5 Diagrams.
Subjects: Alkenes, Ligands (Chemistry), Transition metals, Epimerization, Ethers, Aliphatic alcohols
Abstract: Transition metal–catalyzed cross-couplings have great potential to furnish complex ethers; however, challenges in the C(sp3)–O functionalization step have precluded general methods. Here, we describe computationally guided transition metal–ligand design that positions a hydrogen-bond acceptor anion at the reactive site to promote functionalization. A general cross-coupling of primary, secondary, and tertiary aliphatic alcohols with terminal olefins to furnish >130 ethers is achieved. The mild conditions tolerate functionality that is prone to substitution, elimination, and epimerization and achieve site selectivity in polyol settings. Mechanistic studies support the hypothesis that the ligand’s geometry and electronics direct positioning of the phosphate anion at the π-allyl-palladium terminus, facilitating the phosphate’s hydrogen-bond acceptor role toward the alcohol. Ligand-directed counteranion positioning in cationic transition metal catalysis has the potential to be a general strategy for promoting challenging bimolecular reactivity. [ABSTRACT FROM AUTHOR]
Copyright of Science (pre-March 2025) is the property of American Association for the Advancement of Science and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)
Database: Psychology and Behavioral Sciences Collection
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  Data: Palladium-catalyzed cross-coupling of alcohols with olefins by positional tuning of a counteranion.
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  Data: <searchLink fieldCode="AR" term="%22Kaster%2C+Sven+H%2E+M%2E%22">Kaster, Sven H. M.</searchLink><br /><searchLink fieldCode="AR" term="%22Lei+Zhu%22">Lei Zhu</searchLink><br /><searchLink fieldCode="AR" term="%22Lyon%2C+William+L%2E%22">Lyon, William L.</searchLink><br /><searchLink fieldCode="AR" term="%22Rulin+Ma%22">Rulin Ma</searchLink><br /><searchLink fieldCode="AR" term="%22Ammann%2C+Stephen+E%2E%22">Ammann, Stephen E.</searchLink><br /><searchLink fieldCode="AR" term="%22White%2C+M%2E+Christina%22">White, M. Christina</searchLink>
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  Data: <searchLink fieldCode="JN" term="%22Science+%28pre-March+2025%29%22">Science (pre-March 2025)</searchLink>. 9/6/2024, Vol. 385 Issue 6713, p1067-1076. 10p. 5 Diagrams.
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  Data: <searchLink fieldCode="DE" term="%22Alkenes%22">Alkenes</searchLink><br /><searchLink fieldCode="DE" term="%22Ligands+%28Chemistry%29%22">Ligands (Chemistry)</searchLink><br /><searchLink fieldCode="DE" term="%22Transition+metals%22">Transition metals</searchLink><br /><searchLink fieldCode="DE" term="%22Epimerization%22">Epimerization</searchLink><br /><searchLink fieldCode="DE" term="%22Ethers%22">Ethers</searchLink><br /><searchLink fieldCode="DE" term="%22Aliphatic+alcohols%22">Aliphatic alcohols</searchLink>
– Name: Abstract
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  Data: Transition metal–catalyzed cross-couplings have great potential to furnish complex ethers; however, challenges in the C(sp3)–O functionalization step have precluded general methods. Here, we describe computationally guided transition metal–ligand design that positions a hydrogen-bond acceptor anion at the reactive site to promote functionalization. A general cross-coupling of primary, secondary, and tertiary aliphatic alcohols with terminal olefins to furnish >130 ethers is achieved. The mild conditions tolerate functionality that is prone to substitution, elimination, and epimerization and achieve site selectivity in polyol settings. Mechanistic studies support the hypothesis that the ligand’s geometry and electronics direct positioning of the phosphate anion at the π-allyl-palladium terminus, facilitating the phosphate’s hydrogen-bond acceptor role toward the alcohol. Ligand-directed counteranion positioning in cationic transition metal catalysis has the potential to be a general strategy for promoting challenging bimolecular reactivity. [ABSTRACT FROM AUTHOR]
– Name: AbstractSuppliedCopyright
  Label:
  Group: Ab
  Data: <i>Copyright of Science (pre-March 2025) is the property of American Association for the Advancement of Science and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract.</i> (Copyright applies to all Abstracts.)
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        Value: 10.1126/science.ado8027
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      – Code: eng
        Text: English
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        PageCount: 10
        StartPage: 1067
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      – SubjectFull: Alkenes
        Type: general
      – SubjectFull: Ligands (Chemistry)
        Type: general
      – SubjectFull: Transition metals
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      – SubjectFull: Epimerization
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      – SubjectFull: Ethers
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      – SubjectFull: Aliphatic alcohols
        Type: general
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      – TitleFull: Palladium-catalyzed cross-coupling of alcohols with olefins by positional tuning of a counteranion.
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              M: 09
              Text: 9/6/2024
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              Y: 2024
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