Lewis Acid-Catalyzed Asymmetric [2σ + 2π] Cycloaddition Reactions of Bicyclo[1.1.0]butanes and Vinyl Azido/Diazo Compounds

ACS Catalysis, Год журнала: 2025, Номер unknown, С. 4634 - 4643

Опубликована: Март 4, 2025

Язык: Английский

---

Enantioselective Dearomative [2π + 2σ] Photocycloaddition of Naphthalene Derivatives with Bicyclo[1.1.0]butanes Enabled by Gd(III) Catalysis

Journal of the American Chemical Society, Год журнала: 2025, Номер unknown

Опубликована: Март 28, 2025

The cycloaddition reactions of bicyclo[1.1.0]butanes with alkenes, imines, nitrones, or aziridines have served as an efficient platform to create conformationally restricted saturated bicyclic scaffolds. However, the use readily available aromatics in such reactions, especially asymmetric manner, remains underexplored. Herein, we report a highly regio- and enantioselective dearomative [2π + 2σ] photocycloaddition reaction between naphthalene derivatives bicyclo[1.1.0]butanes, enabled by Gd(III) catalysis. Bicyclo[1.1.0]butanes naphthalenes adorned diverse array functional groups are well-tolerated under mild conditions, affording enantioenriched pharmaceutically important bicyclo[2.1.1]hexanes 30–96% yields 81–93% ee 12:1 → >20:1 rr. synthetic versatility this is further demonstrated facile removal directing group derivatizations dearomatized product. UV–vis absorption spectroscopy studies suggest involvement excited species process.

Язык: Английский

---

FeCl₃-Catalyzed Intermolecular Formal [8π+2σ] Cycloaddition of Azaheptafulvene with Bicyclo[1.1.0]butanes for the Synthesis of Cycloheptatriene-Fused 2-Azabicyclo[3.1.1]heptanes

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Апрель 8, 2025

Higher-order cycloadditions are a simple and effective strategy for constructing significant medium-sized architectures. Azaheptafulvenes reacting with readily accessible bicyclo[1.1.0]butanes (BCBs) through FeCl3-promoted intermolecular formal [8π+2σ] cycloaddition reactions to access cycloheptatriene-fused 2-azabicyclo[3.1.1]heptanes have been developed. This new reaction tolerated wide range of azaheptafulvenes BCBs. Furthermore, the amplification experiment synthetic transformations adducts, including modifications marketed drugs, further highlighted their practicalities. Control experiments DFT calculations suggest that diastereoselective product formation may involve stepwise pathway.

Язык: Английский

---

Catalyst-Controlled Regiodivergent Synthesis of Bicyclo[2.1.1]hexanes via Photochemical Strain-Release Cycloadditions

Journal of the American Chemical Society, Год журнала: 2025, Номер unknown

Опубликована: Апрель 23, 2025

Bicyclo[2.1.1]hexane is an emerging scaffold in various pharmaceutical settings, but the scarcity of approaches to target different regioisomers from a common starting material prevents targeting broader range chemical space. Herein, we demonstrate new design for photocatalyst-controlled regiodivergent synthesis this scaffold. Of particular interest that two distinct substitution patterns was achieved under photochemical conditions with catalyst control. This possible due activating group, N-methylimidazole, not only playing important role guiding divergent pathways also enabling transformation functional groups. Transient absorption spectroscopy discerned between mechanisms, as assignable bands consistent electron transfer and energy processes were distinctively observed, depending on identity photocatalyst.

Язык: Английский

---

Lewis Acid-Catalyzed Enantioselective (4 + 3)/Thia-(3 + 2) Cycloadditions of Bicyclobutanes and Enaminothiones: Catalyst-Directed Divergent Synthesis of Bridged Sulfur Heterocycles

ACS Catalysis, Год журнала: 2025, Номер unknown, С. 7877 - 7890

Опубликована: Апрель 28, 2025

Язык: Английский

---

Recent Advances in Catalytic Asymmetric Transformations of Bicyclobutane: A Versatile Building Block for Enantiopure Bioisosteric Molecules

ACS Catalysis, Год журнала: 2025, Номер unknown, С. 8078 - 8093

Опубликована: Апрель 30, 2025

Язык: Английский

---

Synthesis of Polysubstituted Cyclobutanes through Photoredox Strain-Release/[3,3]-Rearrangement Cascade

Chemical Science, Год журнала: 2025, Номер unknown

Опубликована: Янв. 1, 2025

A photoredox nucleophilic radical strain-release/[3,3]-rearrangement cascade has been established for the synthesis of polysubstituted cyclobutanes by using bicyclo[1.1.0]butanes/cyclobutenes as acceptors and α-silylamines donors.

Язык: Английский

---

Strain-Release-Driven Alder–Ene Reaction of Bicyclo[1.1.0]butanes with β-Fluoroalkyl-α,β-Unsaturated Ketones

The Journal of Organic Chemistry, Год журнала: 2025, Номер unknown

Опубликована: Май 18, 2025

The Alder-ene reaction of the C-C bond in bicyclo[1.1.0]butanes would provide a unique and efficient synthesis route for cyclobutene frameworks. Herein, we report regio- diastereoselective with β-fluoroalkyl-α,β-unsaturated ketones, giving wide variety cyclobutenes two contiguous centers diene products. features atoms step economies exhibits broad substrate scope. Several downstream transformations these were performed.

Язык: Английский

---

Catalyst-Controlled Divergent Synthesis of Bicyclo[2.1.1]hexanes and Cyclobutenes: The Unique Effect of Au(I)

JACS Au, Год журнала: 2025, Номер unknown

Опубликована: Май 22, 2025

Язык: Английский

---