Rhodium‐Catalyzed Homogeneous Enantioselective Transfer Hydrogenation of 1‐Naphthol Derivatives: Solvent‐Tuning of the Chemoselectivity.
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| Title: | Rhodium‐Catalyzed Homogeneous Enantioselective Transfer Hydrogenation of 1‐Naphthol Derivatives: Solvent‐Tuning of the Chemoselectivity. |
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| Authors: | Li, Shan1,2 (AUTHOR), Zhang, Shu‐Xin1 (AUTHOR), He, Yan‐Mei1 (AUTHOR), Li, Ze‐Yu1,2 (AUTHOR), Fan, Qing‐Hua1,2 (AUTHOR) fanqh@iccas.ac.cn |
| Source: | ChemCatChem. 4/15/2025, Vol. 17 Issue 8, p1-9. 9p. |
| Subjects: | Transfer hydrogenation, Homogeneous catalysis, Heterogeneous catalysts, Metal catalysts, Organic synthesis, Hydrogenation |
| Abstract: | In the past several decades, hydrogenation of naphthol derivatives catalyzed by heterogeneous metal catalysts has been widely reported, but precise control of chemo‐, regio‐, and enantioselectivity remains an unresolved challenge. Herein we report the first homogeneous chemo and enantioselective transfer hydrogenation of 1‐naphthol derivatives catalyzed by tethered rhodium‐diamine catalysts with HCOONa reductant affording a broad range of 1‐tetralones and chiral 1,2,3,4‐tetrahydro‐1‐nanphols in high yields with excellent chemo and enantioselectivities, respectively. Preliminary mechanistic study reveals that 1‐naphthol is reduced via a sequential reaction pathway including dearomative tautomerization, 1,4‐hydride addition, and 1,2‐hydride addition in sequence. 1,1,1,3,3,3‐Hexafluoroisopropanol (HFIP) plays vital roles in controlling the reactivity and chemoselectivity of reduction of 1‐naphthols to cyclic ketones. A chemoselectivity switch could be achieved by simply changing the composition of solvent in the second‐step reduction of this one‐pot sequential reaction. This method was applied for the gram‐scale preparation of levobunolol, demonstrating the potential application of this methodology in organic synthesis. [ABSTRACT FROM AUTHOR] |
| Copyright of ChemCatChem is the property of Wiley-Blackwell 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: | Engineering Source |
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| Header | DbId: egs DbLabel: Engineering Source An: 184494551 AccessLevel: 6 PubType: Academic Journal PubTypeId: academicJournal PreciseRelevancyScore: 0 |
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| Items | – Name: Title Label: Title Group: Ti Data: Rhodium‐Catalyzed Homogeneous Enantioselective Transfer Hydrogenation of 1‐Naphthol Derivatives: Solvent‐Tuning of the Chemoselectivity. – Name: Author Label: Authors Group: Au Data: <searchLink fieldCode="AR" term="%22Li%2C+Shan%22">Li, Shan</searchLink><relatesTo>1,2</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Zhang%2C+Shu‐Xin%22">Zhang, Shu‐Xin</searchLink><relatesTo>1</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22He%2C+Yan‐Mei%22">He, Yan‐Mei</searchLink><relatesTo>1</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Li%2C+Ze‐Yu%22">Li, Ze‐Yu</searchLink><relatesTo>1,2</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Fan%2C+Qing‐Hua%22">Fan, Qing‐Hua</searchLink><relatesTo>1,2</relatesTo> (AUTHOR)<i> fanqh@iccas.ac.cn</i> – Name: TitleSource Label: Source Group: Src Data: <searchLink fieldCode="JN" term="%22ChemCatChem%22">ChemCatChem</searchLink>. 4/15/2025, Vol. 17 Issue 8, p1-9. 9p. – Name: Subject Label: Subjects Group: Su Data: <searchLink fieldCode="DE" term="%22Transfer+hydrogenation%22">Transfer hydrogenation</searchLink><br /><searchLink fieldCode="DE" term="%22Homogeneous+catalysis%22">Homogeneous catalysis</searchLink><br /><searchLink fieldCode="DE" term="%22Heterogeneous+catalysts%22">Heterogeneous catalysts</searchLink><br /><searchLink fieldCode="DE" term="%22Metal+catalysts%22">Metal catalysts</searchLink><br /><searchLink fieldCode="DE" term="%22Organic+synthesis%22">Organic synthesis</searchLink><br /><searchLink fieldCode="DE" term="%22Hydrogenation%22">Hydrogenation</searchLink> – Name: Abstract Label: Abstract Group: Ab Data: In the past several decades, hydrogenation of naphthol derivatives catalyzed by heterogeneous metal catalysts has been widely reported, but precise control of chemo‐, regio‐, and enantioselectivity remains an unresolved challenge. Herein we report the first homogeneous chemo and enantioselective transfer hydrogenation of 1‐naphthol derivatives catalyzed by tethered rhodium‐diamine catalysts with HCOONa reductant affording a broad range of 1‐tetralones and chiral 1,2,3,4‐tetrahydro‐1‐nanphols in high yields with excellent chemo and enantioselectivities, respectively. Preliminary mechanistic study reveals that 1‐naphthol is reduced via a sequential reaction pathway including dearomative tautomerization, 1,4‐hydride addition, and 1,2‐hydride addition in sequence. 1,1,1,3,3,3‐Hexafluoroisopropanol (HFIP) plays vital roles in controlling the reactivity and chemoselectivity of reduction of 1‐naphthols to cyclic ketones. A chemoselectivity switch could be achieved by simply changing the composition of solvent in the second‐step reduction of this one‐pot sequential reaction. This method was applied for the gram‐scale preparation of levobunolol, demonstrating the potential application of this methodology in organic synthesis. [ABSTRACT FROM AUTHOR] – Name: AbstractSuppliedCopyright Label: Group: Ab Data: <i>Copyright of ChemCatChem is the property of Wiley-Blackwell 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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| RecordInfo | BibRecord: BibEntity: Identifiers: – Type: doi Value: 10.1002/cctc.202402081 Languages: – Code: eng Text: English PhysicalDescription: Pagination: PageCount: 9 StartPage: 1 Subjects: – SubjectFull: Transfer hydrogenation Type: general – SubjectFull: Homogeneous catalysis Type: general – SubjectFull: Heterogeneous catalysts Type: general – SubjectFull: Metal catalysts Type: general – SubjectFull: Organic synthesis Type: general – SubjectFull: Hydrogenation Type: general Titles: – TitleFull: Rhodium‐Catalyzed Homogeneous Enantioselective Transfer Hydrogenation of 1‐Naphthol Derivatives: Solvent‐Tuning of the Chemoselectivity. Type: main BibRelationships: HasContributorRelationships: – PersonEntity: Name: NameFull: Li, Shan – PersonEntity: Name: NameFull: Zhang, Shu‐Xin – PersonEntity: Name: NameFull: He, Yan‐Mei – PersonEntity: Name: NameFull: Li, Ze‐Yu – PersonEntity: Name: NameFull: Fan, Qing‐Hua IsPartOfRelationships: – BibEntity: Dates: – D: 15 M: 04 Text: 4/15/2025 Type: published Y: 2025 Identifiers: – Type: issn-print Value: 18673880 Numbering: – Type: volume Value: 17 – Type: issue Value: 8 Titles: – TitleFull: ChemCatChem Type: main |
| ResultId | 1 |
