Lewis Acid-Catalyzed 1,3-Dipolar Cycloaddition of Bicyclobutanes with Isatogens: Access to Tetracyclic 2-Oxa-3-azabicyclo[3.1.1]heptanes DOI Creative Commons

Shiksha Deswal,

Rohan Chandra Das,

Deeptanu Sarkar

et al.

JACS Au, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 19, 2024

The 'escape from flatland' concept has gained significant traction in modern drug discovery, emphasizing the importance of three-dimensional molecular architectures, which serve as saturated bioisosteres benzenoids. Bicyclo[1.1.0]butanes (BCBs), known for their high ring strain and numerous reactivities, offer a simple yet effective method synthesizing these bicyclic frameworks. Although (3 + 2) annulations involving BCBs have been extensively studied, 1,3-dipolar cycloaddition leading to 3) annulation received limited attention. Herein, we report Lewis acid-catalyzed with isatogens allowing synthesis biologically relevant tetracyclic 2-oxa-3-azabicyclo[3.1.1]heptanes. Moreover, reaction can be performed one-pot process by situ generation 2-alkynylated nitrobenzenes. Additionally, preliminary mechanistic photophysical studies annulated products experiments toward asymmetric version this are also provided.

Language: Английский

Copper(II)-Catalyzed Asymmetric (3+3) Annulation of Diaziridines with Oxiranes DOI
Ying Hu,

Heng-Bin Yu,

Tian Yin

et al.

Organic Letters, Journal Year: 2025, Volume and Issue: 27(5), P. 1310 - 1315

Published: Jan. 29, 2025

Highly asymmetric (3+3) annulation of diaziridines with oxiranes via C-N bond cleavage in diaziridine was achieved under 10 mol % chiral copper(II) complex as the catalyst mild reaction conditions. With Cu(OTf)2 Lewis acid and C1-symmetric imidazolidine-pyrroloimidazolone pyridine ligand, diverse tetrahydro-[1,3,4]-oxadiazines were obtained by stereospecific C-N/C-O formation moderate to good yields (up 93% yield) high diastereo- (>20:1 dr) enantioselectivities 92% ee). The catalytic cycle stereochemical model proposed DFT calculation.

Language: Английский

Citations

0
Enantioselective [2π + 2σ] cycloaddition of bicyclobutanes with imines: An efficient approach to chiral 2-aza-bicyclo[2.1.1]hexanes DOI

Xuan-Ge Zhang,

Junjia Chen,

Zi-Yang Zhou

et al.

Chem Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 101295 - 101295

Published: March 1, 2025

Language: Английский

Citations

0
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

et al.

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: March 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.

Language: Английский

Citations

0
Conditions-Controlled Divergent Annulation of Bicyclo[1.1.0]butanes and Dioxopyrrolidines through Lewis Acid Catalysis DOI
Jun‐Long Li, Chuan Xie, Rong Zeng

et al.

ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 6025 - 6035

Published: March 28, 2025

Language: Английский

Citations

0
Lewis Acid-Catalyzed 1,3-Dipolar Cycloaddition of Bicyclobutanes with Isatogens: Access to Tetracyclic 2-Oxa-3-azabicyclo[3.1.1]heptanes DOI Creative Commons

Shiksha Deswal,

Rohan Chandra Das,

Deeptanu Sarkar

et al.

JACS Au, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 19, 2024

The 'escape from flatland' concept has gained significant traction in modern drug discovery, emphasizing the importance of three-dimensional molecular architectures, which serve as saturated bioisosteres benzenoids. Bicyclo[1.1.0]butanes (BCBs), known for their high ring strain and numerous reactivities, offer a simple yet effective method synthesizing these bicyclic frameworks. Although (3 + 2) annulations involving BCBs have been extensively studied, 1,3-dipolar cycloaddition leading to 3) annulation received limited attention. Herein, we report Lewis acid-catalyzed with isatogens allowing synthesis biologically relevant tetracyclic 2-oxa-3-azabicyclo[3.1.1]heptanes. Moreover, reaction can be performed one-pot process by situ generation 2-alkynylated nitrobenzenes. Additionally, preliminary mechanistic photophysical studies annulated products experiments toward asymmetric version this are also provided.

Language: Английский

Citations

2