Highly Regio‐ and Enantioselective Cu/Pd Co‐Catalyzed Allylic Alkylation of α‐pyridyl‐α‐fluoroesters: Construction of Quaternary C−F Stereocenters

Yan, Xinlong; Li, Zongwei; Fan, Lin; Li, Jiashan; Liu, Guodu

doi:10.1002/asia.202300160

Cited by 6 publications

(2 citation statements)

References 53 publications

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“…In 2023, we described the regio- and enantioselective allylic alkylation of α-pyridyl-α-fluoroesters with allyl acetates promoted by Cu/Pd synergistic catalysis, constructing carbon–fluorine quaternary stereocenters (Scheme 39). 46 In this co-catalytic system, the palladium catalyst mainly constructed the C–C bond, while the chiral copper catalyst controlled the enantioselectivity. A series of aryl- and aliphatic-substituted allyl acetates were applied, giving the corresponding products in high yield, with excellent enantioselectivity and E / Z ratio (up to 98% yield, 98 : 2 er, E / Z > 20 : 1).…”

Section: Asymmetric Allylation Of Fluorinated Substratesmentioning

confidence: 99%

Recent advances in stereoselective construction of fluorinated quaternary carbon centers from fluorinated compounds

Li,

Fan,

Liu

2024

Org. Biomol. Chem.

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Section: Asymmetric Allylation Of Fluorinated Substratesmentioning

confidence: 99%

Recent advances in stereoselective construction of fluorinated quaternary carbon centers from fluorinated compounds

Li,

Fan,

Liu

2024

Org. Biomol. Chem.

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“…Originating from independent research in 1995 by Richards [ 1 ], Sammakia [ 2 ], and Uemura’s [ 3 ] groups, chiral ligands based on the oxazoline ferrocene backbone have played a pivotal role in diverse transition metal-catalyzed asymmetric reactions over the past three decades, ranging from academic laboratory researches to industrial productions [ 4 , 5 , 6 ], with more than 600 publications and patents attesting to their significance. Even today, chiral oxazoline phosphine ferrocene ligands ( FOXAP s) remain the preferred choice for many emerging reactions aimed at achieving highly stereoselective products [ 7 , 8 , 9 , 10 , 11 , 12 , 13 , 14 , 15 , 16 , 17 , 18 , 19 , 20 , 21 , 22 ].…”

Section: Introductionmentioning

confidence: 99%

Enhancing the Efficacy of Chiral Ligands and Catalysts: Siloxane-Substituted Oxazoline Ferrocenes as Next-Generation Candidates

Dai,

Zhao,

et al. 2024

Molecules

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Since the discovery of classical chiral oxazoline ferrocene ligands in 1995, they have become pivotal in transition metal-catalyzed asymmetric transformations. Over the past decade, a notable evolution has been observed with the emergence of siloxane-substituted oxazoline ferrocenes, demonstrating significant potential as chiral ligands and catalysts. These compounds have consistently delivered exceptional results in diverse and mechanistically distinct transformations, surpassing the capabilities of classical oxazoline ferrocene ligands. This review meticulously delineates the research progress on siloxane-substituted oxazoline ferrocene compounds. It encompasses the synthesis of crucial precursors and desired products, highlights their achievements in asymmetric catalysis reactions, and delves into the exploration of the derivatization of these compounds, emphasizing the introduction of ionophilic groups and their impact on the recovery of transition metal catalysts. In addition to presenting the current state of knowledge, this review propels future research directions by identifying potential topics for further investigation concerning the siloxane-tagged derivatives. These derivatives are poised to be promising candidates for the next generation of highly efficient ligands and catalysts.

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The Catalytic Asymmetric Allylic Alkylation of Acyclic Enolates for the Construction of Quaternary and Tetrasubstituted Stereogenic Centres

Griffiths,

Franckevičius

2024

Chemistry A European J

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To facilitate the discovery and development of new pharmaceuticals, the demand for novel stereofunctionalised building blocks has never been greater. Whilst molecules bearing quaternary and tetrasubstituted stereogenic centres are ideally suited to explore untapped areas of chemical space, the asymmetric construction of sterically congested carbon centres remains a longstanding challenge in organic synthesis. The enantioselective assembly of acyclic stereogenic centres is even more demanding due to the need to restrict a much wider range of geometries and conformations of the intermediates involved. In this context, the catalytic asymmetric allylic alkylation (AAA) of acyclic prochiral nucleophiles, namely enolates, has become an indispensable tool to access a range of linear α‐quaternary and α‐tetrasubstituted carbonyl compounds. However, unlike the AAA of cyclic enolates with a fixed enolate geometry, to achieve high levels of stereocontrol in the AAA of acyclic enolates, the stereoselectivity of enolisation must be considered. The aim of this review is to offer a comprehensive discussion of catalytic AAA reactions of acyclic prochiral enolates and their analogues to generate congested quaternary and tetrasubstituted chiral centres using metal, non‐metal and dual catalysis, with particular focus given to the control of enolate geometry and its impact on the stereochemical outcome of the reaction.

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Highly Regio‐ and Enantioselective Cu/Pd Co‐Catalyzed Allylic Alkylation of α‐pyridyl‐α‐fluoroesters: Construction of Quaternary C−F Stereocenters

Cited by 6 publications

References 53 publications

Recent advances in stereoselective construction of fluorinated quaternary carbon centers from fluorinated compounds

Recent advances in stereoselective construction of fluorinated quaternary carbon centers from fluorinated compounds

Enhancing the Efficacy of Chiral Ligands and Catalysts: Siloxane-Substituted Oxazoline Ferrocenes as Next-Generation Candidates

The Catalytic Asymmetric Allylic Alkylation of Acyclic Enolates for the Construction of Quaternary and Tetrasubstituted Stereogenic Centres

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