Rhodium‐Catalyzed Asymmetric Arylation of Cyclobutenone Ketals

Egea-Arrebola, David; Goetzke, F. Wieland; Fletcher, Stephen P.

doi:10.1002/anie.202217381

Cited by 9 publications

(2 citation statements)

References 32 publications

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“…In 2023, Fletcher and colleagues reported a rhodiumcatalyzed cross-coupling reaction of cyclobutenone ketals 207 with organoboronic acids 208, which offered enantioenriched cyclobutenyl ethers 209 in good to excellent yields and enantioselectivities (Scheme 36, top). [49] This reaction pathway likely begins with transmetalation and olefin insertion, followed by β-oxygen elimination and protonation to furnish the expected products. As expected, olefin insertion was the regioand enantio-determining step with the assistance of a chiral diene ligand 210.…”

Section: Enantioselective Functionalization Of Four-membered Carbocyclesmentioning

confidence: 99%

Recent Advances in Asymmetric Synthesis of Chiral Cyclobutenes

Hu,

Zhao,

Che

et al. 2024

ChemCatChem

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Cyclobutene scaffolds occur in natural products and bioactive compounds. Their unique structural features and intrinsic ring strain make cyclobutene a type of important building block in synthetic chemistry. In recent years, considerable efforts have been dedicated to the synthesis of chiral cyclobutenes. Enantioselective [2+2] cycloadditions and functionalization of cyclobutene derivatives have emerged as powerful and reliable protocols for achieving this goal, resulting in significant progress in this field. This review provides a comprehensive summary of the recent advancements in the asymmetric synthesis of chiral cyclobutenes, and the discussion is logically divided into four parts according to the reaction mode.

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Section: Enantioselective Functionalization Of Four-membered Carbocyclesmentioning

confidence: 99%

Recent Advances in Asymmetric Synthesis of Chiral Cyclobutenes

Hu,

Zhao,

Che

et al. 2024

ChemCatChem

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“…From a synthetic perspective, the precise functionalization of common cyclobutene derivatives could enable a divergent approach to prepare four-membered ring molecules with versatile chemical structure space. As a class of readily available carbocycles, cyclobutene has been used to synthesize enantioenriched cyclobutane derivatives with the catalysis of Cu, , Pt, Rh, , and Co . An elegant rhodium-catalyzed asymmetric addition of cyclobutenes with arylboronic acids has been reported to provide hydroarylation product Pattern A cyclobutanes, and a highly enantioselective difunctionalization of cyclobutenes for the syntheses of Pattern B and C cyclobutanes is still underdeveloped.…”

Section: Introductionmentioning

confidence: 99%

Palladium-Catalyzed Divergent Enantioselective Functionalization of Cyclobutenes

Wang,

Zhu,

Wang

et al. 2024

J. Am. Chem. Soc.

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Aliphatic strained rings have been increasingly applied in medicinal chemistry due to their beneficial physicochemical and pharmacokinetic properties. However, the divergent synthesis of enantioenriched cyclobutane derivatives with various structural patterns continues to be a significant challenge. Here, we disclose a palladium-catalyzed enantioselective desymmetrization of cyclobutenes, resulting in a series of hydroarylation and 1,2- and 1,3-diarylation products via the interceptions of a common Heck intermediate. Mechanistic investigations provide valuable insights into understanding the catalytic mode of the palladium catalysts and the observed variations in the deuterium-responsive behavior during reactions. Furthermore, the synthetic utility is demonstrated in the syntheses of deuterated drug candidate belaperidone skeletons and pseudosymmetrical truxinic acid-type derivatives.

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Nickel‐Catalyzed Tunable Enantioconvergence and Kinetic Resolution in the Coupling of Tertiary Cyclobutenols with Arylboroxines

2023

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We report that a nickel catalyst system with a modified 1,1′‐spirobiindane‐7,7′‐diol‐phosphoramidite (SPINOL) as the chiral ligand can enable the coupling of tertiary cyclobutenols and arylboroxines in an enantioconvergent manner, providing cyclobutenes with an all‐carbon quaternary stereocenter in good yields (up to 84 % yield) with excellent enantioselectivities (up to >99 % ee). Moreover, the catalytic system can be applied in the kinetic resolution of cyclobutenols under slightly modified conditions, giving enantioenriched tertiary cyclobutenols with an s factor of up to >200. The reaction uses free hydroxyl groups as the leaving group without additional activation while the strained ring remains untouched. Preliminary mechanistic studies reveal that the inherent discrepant reactivity of the two enantiomers is the key to the controllable enantioconvergent and kinetic resolution process.

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Rhodium‐Catalyzed Asymmetric Arylation of Cyclobutenone Ketals

Cited by 9 publications

References 32 publications

Recent Advances in Asymmetric Synthesis of Chiral Cyclobutenes

Recent Advances in Asymmetric Synthesis of Chiral Cyclobutenes

Palladium-Catalyzed Divergent Enantioselective Functionalization of Cyclobutenes

Nickel‐Catalyzed Tunable Enantioconvergence and Kinetic Resolution in the Coupling of Tertiary Cyclobutenols with Arylboroxines

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