Enantioselective [2π + 2σ] Cycloadditions of Bicyclo[1.1.0]butanes with Vinylazaarenes through Asymmetric Photoredox Catalysis

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(12), P. 8372 - 8380

Published: March 18, 2024

Here we present a highly enantioselective [2π + 2σ] photocycloaddition of bicyclo[1.1.0]butanes (BCBs). The reaction uses variety vinylazaarenes as partners and is catalyzed by polycyclic aromatic hydrocarbon (PAH)-containing chiral phosphoric acid bifunctional photosensitizer. A wide array pharmaceutically important bicyclo[2.1.1]hexane (BCH) derivatives have been synthesized with high yields, enantioselectivity, diastereoselectivity. In addition to the diverse 1-ketocarbonyl-3-substituted BCBs, α/β-substituted are compatible such an unprecedented photoredox catalytic pathway, resulting in successful assembly all-carbon quaternary stereocenter or two adjacent tertiary stereocenters on product.

Language: Английский

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Three-dimensional saturated C(sp3)-rich bioisosteres for benzene

Nature Reviews Chemistry, Journal Year: 2024, Volume and Issue: 8(8), P. 605 - 627

Published: July 9, 2024

Language: Английский

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Enantioselective synthesis of 2-substituted bicyclo[1.1.1]pentanes via sequential asymmetric imine addition of bicyclo[1.1.0]butanes and skeletal editing

Nature Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 28, 2025

Language: Английский

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Pyridine-boryl radical-catalyzed [3π + 2σ] cycloaddition for the synthesis of pyridine isosteres

Chem, Journal Year: 2024, Volume and Issue: unknown

Published: Sept. 1, 2024

Language: Английский

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Palladium-catalysed [2σ + 2π] cycloaddition reactions of bicyclo[1.1.0]butanes with aldehydes

Nature Synthesis, Journal Year: 2024, Volume and Issue: unknown

Published: Sept. 27, 2024

Language: Английский

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Difunctionalization of bicyclo[1.1.0]butanes enabled by merging C−C cleavage and ruthenium-catalysed remote C−H activation

Nature Synthesis, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 17, 2025

Language: Английский

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Palladium-catalyzed enantioselective [2σ + 2π] cycloadditions of vinyl-carbonyl-bicyclo[1.1.0]butanes with arylidenemalononitriles

Chinese Chemical Letters, Journal Year: 2025, Volume and Issue: unknown, P. 111072 - 111072

Published: March 1, 2025

Language: Английский

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Recent Progress in Accessing Multi-functionalized Caged Hydrocarbons: En Route to Highly Functionalized Saturated (Bio)isosteres of Benzene Rings

Synthesis, Journal Year: 2024, Volume and Issue: unknown

Published: July 4, 2024

Abstract Recently, many saturated bioisosteres of the benzene ring have been developed, and their applications in drug development evaluated. Most these are caged hydrocarbons, which rigid skeletons three-dimensional spaces. Recent efforts to synthesize hydrocarbons enabled access multi-functionalized congeners that expected be (bio)isosteres benzenes. This short review summarizes recently reported methods for obtaining (typically more than disubstituted) hydrocarbons. 1 Introduction 2 Proposed Structures Caged Hydrocarbons as Saturated (Bio)isosteres Benzene Ring: A Brief Summary 3 Access Multi-functionalized Hydrocarbons: De Novo Synthetic Approaches 3.1 Bicyclo[1.1.1]pentanes (BCPs) 3.2 Bicyclo[2.1.1]hexanes (BCHs) 3.3 Bicyclo[3.1.1]heptanes (BCHeps) 3.4 Others 4 C–H Functionalization 5 Conclusion

Language: Английский

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Pyridine-Boryl Radical-Catalyzed [3π + 2σ] Cycloaddition for the Synthesis of Pyridine Bioisosteres

Published: April 1, 2024

The exploration of C(sp3)-rich three-dimensional (3D) scaffolds as bioisosteres for planar aromatics has garnered increasing attention. While the bioisosterism benzenes been extensively studied, pyridines, second most prevalent aromatic compounds in pharmaceuticals, faces additional challenges and encountered surprisingly limited success. In this study, we propose unprecedented 2-azabicyclo[3.1.1]heptenes effective 1,3,5-trisubstituted pyridines terms not only 3D conformation but also basicity. We develop a pyridine-boryl radical-catalyzed [3π + 2σ] cycloaddition reaction vinyl azides with bicyclo[1.1.0]butanes (BCBs) an efficient synthetic approach. Synthetic manipulation products reveals valuable handles, allowing modular synthesis various pyridine bioisosteres.

Language: Английский

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Enantioselective Synthesis of β-Aminoboronic Acids via Borylalkylation of Enamides

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(24), P. 16639 - 16647

Published: June 10, 2024

Aminoboronic acids represent a class of significant compounds that have attracted attention in the fields drug discovery and organic synthesis. Despite notable progress their synthesis, efficient construction chiral β-aminoboronic with alkyl side chains remains challenging endeavor. Here, we introduce an unprecedented nickel-catalyzed asymmetric borylalkylation enamides, employing simple diamine ligand, readily available B2pin2, halides as coupling partners. This reaction serves platform for assembling diverse range acid derivatives flexible chains, displaying exceptional regio-, stereo-, enantioselectivities. Moreover, this transformation exhibits broad substrate scope remarkable tolerance toward various functional groups. Theoretical calculations demonstrate benzyl group on ligand is key to high enantiocontrol transformation. Additionally, exemplify practical application strategy through concise synthesis complex bioactive molecules.

Language: Английский

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