Strain-Release-Driven Alder–Ene Reaction of Bicyclo[1.1.0]butanes with β-Fluoroalkyl-α,β-Unsaturated Ketones DOI
Wenjie Xu, Zhiyi Zhang, Hao Wu

и другие.

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

Enantioselective Dearomative [2π + 2σ] Photocycloaddition of Naphthalene Derivatives with Bicyclo[1.1.0]butanes Enabled by Gd(III) Catalysis DOI
Wenjie Shen, Xiaoqin Zou, Muzi Li

и другие.

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

Процитировано

1
Regio- and Diastereoselective Cascade Reactions of Bicyclo[1.1.0]butanes: Access to gem-Difluorinated Carbocyclic Rings DOI
Zhiyi Zhang, Hao Wu, Wenjie Xu

и другие.

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Апрель 17, 2025

gem-Difluorinated carbocyclic rings are attractive motifs in drug development. Herein, we report the transition-metal free cascade reaction of bicyclo[1.1.0]butanes (BCBs) with gem-difluorocyclopropenes for synthesis gem-difluorinated excellent regio- and diastereoselectivity. This method was successfully applied to provide a broad range cyclopentenes cyclopropanes, which could undergo variety difluoromethylene (CF2) retaining transformations.

Язык: Английский

Процитировано

1
Enantioselective dearomative formal (3+3) cycloadditions of bicyclobutanes with aromatic azomethine imines: access to fused 2,3-diazabicyclo[3.1.1]heptanes DOI Creative Commons
Xue-Chun Yang, Feng Wu, Wen‐Biao Wu

и другие.

Chemical Science, Год журнала: 2024, Номер 15(46), С. 19488 - 19495

Опубликована: Янв. 1, 2024

We present the first enantioselective dearomative (3+3) cycloadditions of bicyclobutanes (BCBs) utilizing a chiral Lewis acid catalyst and bidentate chelating BCB substrates.

Язык: Английский

Процитировано

7
3-Oxabicyclo[3.1.1]heptanes as Isosteres of meta-Substituted Benzene Rings DOI
Jennifer Morvan, Evelien Renders, Peter Buijnsters

и другие.

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Март 20, 2025

Replacement of the aromatic rings in drug candidates with isosteric rigid sp3-rich scaffolds can improve physicochemical properties, increase chance progressing molecule development, and open new chemical space. Isosteres meta-substituted benzenes remain challenging due to difficulty mimicking exit vector angles bond distances. Herein, we report synthesis 1,5-disubstituted 3-oxabicyclo[3.1.1]heptanes (oxa-BCHeps), which serve as saturated isosteres phenyl a similar geometric arrangement. This structural motif be obtained under mild reaction conditions via acid-mediated isomerization (2-oxaspiro[3.3]heptan-6-yl)methanols using catalytic quantities pyridinium chloride (PyrHCl). We demonstrate utility this methodology by preparing various building blocks for use medicinal chemistry incorporating 3-oxa-BCHep into anticancer sonidegib, improving its such permeability, metabolic stability, solubility.

Язык: Английский

Процитировано

0
Synthesis of 2,5-Dithia-bicyclo[4.1.1]octanes by Silver-Catalyzed Formal (4+3) Cycloadditions of Bicyclobutanes with Benzodithioloimines DOI

Xuechen Zhou,

Jianyang Dong,

Huijuan Liao

и другие.

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Март 30, 2025

Cycloadditions of bicyclobutanes with two- or three-atom reaction partners have been widely exploited to access bicyclo[2.1.1]hexanes and bicyclo[3.1.1]heptanes. However, their application the synthesis bicyclo[4.1.1]octane derivatives has remained elusive. Herein, we report silver-catalyzed formal (4+3) cycloadditions between simple benzodithioloimines, establishing a new method for synthesizing previously inaccessible 2,5-dithia-bicyclo[4.1.1]octanes, which two sulfur atoms in frameworks. This mild tolerates bicyclobutane substrates wide range substituents. The synthetic utility this was demonstrated via various transformations products yield valuable sulfur-containing bridged bicyclic scaffolds.

Язык: Английский

Процитировано

0
Catalyst-Controlled Regiodivergent Synthesis of Bicyclo[2.1.1]hexanes via Photochemical Strain-Release Cycloadditions DOI
Yu‐Che Chang, María Martín,

Kingsley Bortey

и другие.

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

Процитировано

0
Recent Advances in Catalytic Asymmetric Transformations of Bicyclobutane: A Versatile Building Block for Enantiopure Bioisosteric Molecules DOI
Yejin Koo, Jinwook Jeong, Sungwoo Hong

и другие.

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

Опубликована: Апрель 30, 2025

Язык: Английский

Процитировано

0
Strain-Release-Driven Alder–Ene Reaction of Bicyclo[1.1.0]butanes with β-Fluoroalkyl-α,β-Unsaturated Ketones DOI
Wenjie Xu, Zhiyi Zhang, Hao Wu

и другие.

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

Процитировано

0