4.8 Article

Pyridine-Boryl Radical-Catalyzed [2?+2?] Cycloaddition of Bicyclo[1.1.0]butanes with Alkenes

相关参考文献

注意:仅列出部分参考文献,下载原文获取全部文献信息。
Article Chemistry, Multidisciplinary

Selective [2σ+2σ] Cycloaddition Enabled by Boronyl Radical Catalysis: Synthesis of Highly Substituted Bicyclo[3.1.1]heptanes

Tao Yu et al.

Summary: In this study, a novel [2 sigma + 2 sigma] radical cycloaddition reaction between bicyclo[1.1.0]butanes (BCBs) and cyclopropyl ketones was developed. This reaction provides a modular, concise, and atom-economical synthetic route to substituted bicyclo[3.1.1]heptane (BCH) derivatives, which are 3D bioisosteres of benzenes and core skeleton of terpene natural products. The reaction was catalyzed by a combination of tetraalkoxydiboron(4) compound B(2)pin(2) and 3-pentyl isonicotinate. The broad substrate scope was demonstrated by synthesizing highly functionalized BCHs with up to six substituents on the core and up to 99% isolated yield. Computational mechanistic investigations supported a pyridine-assisted boronyl radical catalytic cycle.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2023)

Article Chemistry, Multidisciplinary

A catalytic alkene insertion approach to bicyclo[2.1.1]hexane bioisosteres

Soumitra Agasti et al.

Summary: A general synthetic route to substituted bicyclo[2.1.1]hexanes (BCHs) has been developed through intermolecular coupling between olefins and bicyclo[1.1.0]butyl (BCB) ketones. The SmI2-catalysed process can be applied to a wide range of electron-deficient alkenes and substituted BCB ketones, with low loadings of SmI2. The resulting BCH ketones have been shown to be versatile synthetic intermediates and can be used for selective downstream manipulation and the expedient synthesis of a saturated hydrocarbon analogue of the broad-spectrum antimicrobial, phthalylsulfathiazole.

NATURE CHEMISTRY (2023)

Article Chemistry, Organic

Investigating Bicyclobutane-Triazolinedione Cycloadditions as a Tool for Peptide Modification

Brett D. Schwartz et al.

Summary: This study investigates the strain promoted cycloaddition reactions of acyl bicyclobutanes with triazolinedione reagents. The synthesis of novel peptide conjugates through cycloaddition reactions is facilitated by the orthogonally protected urazole building block. The additive-free and fully atom-economical nature of this transformation provides a promising starting point for the functionalization of biomolecules.

ORGANIC LETTERS (2022)

Article Chemistry, Multidisciplinary

Beyond Bioisosteres: Divergent Synthesis of Azabicyclohexanes and Cyclobutenyl Amines from Bicyclobutanes

Kushal Dhake et al.

Summary: The development of two divergent and complementary Lewis acid catalyzed additions of bicyclobutanes to imines is described. Microscale high-throughput experimentation was integral to the discovery and optimization of both reactions. N-arylimines undergo formal (3+2) cycloaddition with bicyclobutanes to yield azabicyclo[2.1.1]hexanes in a single step; in contrast, N-alkylimines undergo an addition/elimination sequence to generate cyclobutenyl methanamine products with high diastereoselectivity. These new products contain a variety of synthetic handles for further elaboration, including many functional groups relevant to pharmaceutical synthesis. The divergent reactivity observed is attributed to differences in basicity and nucleophilicity of the nitrogen atom in a common carbocation intermediate, leading to either nucleophilic attack (N-aryl) or E1 elimination (N-alkyl).

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2022)

Article Chemistry, Multidisciplinary

Asymmetric Defluoroallylation of 4-Trifluoromethylpyridines Enabled by Umpolung C-F Bond Activation

Fei-Yu Zhou et al.

Summary: Carbon-fluorine bond activation of trifluoromethyl group is an important synthetic method. Although selective defluorinative functionalization of trifluoromethyl substrates has been achieved, transformations via fluorocarbanion mechanism still face challenges. In this study, a new method for the asymmetric defluoroallylation of trifluoromethylpyridine has been developed.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2022)

Article Chemistry, Multidisciplinary

Catalysis with Diboron(4)/Pyridine: Application to the Broad-Scope[3+2] Cycloaddition of Cyclopropanes and Alkenes

Zhengwei Ding et al.

Summary: This study reports an economical reaction using commercial diboron(4) as a catalyst. By designing a catalytic cycle and using a pyridine cocatalyst, boronyl radicals can be generated and transferred reversibly. The reaction features metal-free conditions, inexpensive and stable catalysts, simple operation, and a broad substrate scope compared to transition metal-based catalysts.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2022)

Article Chemistry, Multidisciplinary

Strain-Release [2π+2σ] Cycloadditions for the Synthesis of Bicyclo[2.1.1]hexanes Initiated by Energy Transfer

Renyu Guo et al.

Summary: Saturated bicycles are increasingly important in the design and development of new pharmaceuticals. This article describes a new strategy for synthesizing bicyclo[2.1.1]hexanes, which have defined exit vectors but are underexplored as building blocks in terms of substitution patterns. The process involves sensitization of a bicyclo[1.1.0]butane followed by cycloaddition with an alkene. The scope and mechanistic details of the method are discussed.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2022)

Article Multidisciplinary Sciences

Intermolecular [2π+2σ]-photocycloaddition enabled by triplet energy transfer

Roman Kleinmans et al.

Summary: In this study, a new intermolecular [2+2]-photocycloaddition method using bicyclo[1.1.0]butanes as 2 sigma-electron reactants was reported. This reaction was realized by visible-light-mediated triplet energy transfer catalysis. The method allows for a simple, modular, and diastereoselective synthesis of bicyclo[2.1.1]hexanes and extends to a-bonds, providing previously inaccessible structural motifs.

NATURE (2022)

Article Chemistry, Multidisciplinary

Photochemical Intermolecular [3Σ+2Σ]-Cycloaddition for the Construction of Aminobicyclo[3.1.1]heptanes

Yongxiang Zheng et al.

Summary: In this study, we have disclosed the first photoinduced [3 sigma + 2 sigma] cycloaddition for the synthesis of trisubstituted bicyclo[3.1.1]heptanes using bicyclo[1.1.0]butanes and cyclopropylamines. This method offers mild and operationally simple conditions, along with unique meta-substituted arene bioisosteres.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2022)

Article Chemistry, Multidisciplinary

Synthesis of Polysubstituted 2-Oxabicyclo[2.1.1]hexanes via Visible- Light-Induced Energy Transfer

Yujie Liang et al.

Summary: The synthesis of polysubstituted 2-oxabicyclo[2.1.1]hexanes has been achieved in a single step using visible-light-induced triplet energy transfer catalysis. This method offers significant potential in pharmaceutical development, allowing for the rapid construction of complex molecular structures and access to unexplored chemical space.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2022)

Article Chemistry, Multidisciplinary

Diboron(4)-Catalyzed Remote [3+2] Cycloaddition of Cyclopropanes via Dearomative/Rearomative Radical Transmission through Pyridine

Ming Xu et al.

Summary: This study developed a novel method for selective activation of a remote bond using a through-(hetero)arene radical transmission concept. By a metal-free [3+2] cycloaddition reaction, pyridine-substituted cyclopentanes, cyclopentenes, and bicyclo[2.1.1]hexanes that are difficult to access using known methods were synthesized. The reaction was catalyzed by a simple and inexpensive diboron(4) compound and proceeded via dearomative/rearomative processes.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2022)

Article Chemistry, Medicinal

Bioisosteres of the Phenyl Ring: Recent Strategic Applications in Lead Optimization and Drug Design

Murugaiah A. M. Subbaiah et al.

Summary: The benzene moiety is commonly found in drugs, but its indiscriminate use can lead to poor physicochemical properties. Bioisosteric replacements for benzene rings can improve potency, solubility, and metabolic stability while reducing lipophilicity and other negative effects.

JOURNAL OF MEDICINAL CHEMISTRY (2021)

Article Chemistry, Organic

Recent Developments in Transition-Metal-Free Functionalization and Derivatization Reactions of Pyridines

Fei-Yu Zhou et al.

Summary: This review provides a brief summary of recent advances in transition-metal-free functionalization and derivatization reactions of pyridines, organized according to their reaction modes.

SYNLETT (2021)

Article Chemistry, Multidisciplinary

Photoinduced Radical Borylation of Alkyl Bromides Catalyzed by 4-Phenylpyridine

Li Zhang et al.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2020)

Article Chemistry, Multidisciplinary

Enantioselective Reductive Coupling of Imines Templated by Chiral Diboron

Mingkang Zhou et al.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2020)

Article Chemistry, Multidisciplinary

Saturated Bioisosteres ofortho-Substituted Benzenes

Aleksandr Denisenko et al.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2020)

Article Chemistry, Medicinal

Analysis of Benzenoid Substitution Patterns in Small Molecule Active Pharmaceutical Ingredients

Aleksandra Nilova et al.

JOURNAL OF MEDICINAL CHEMISTRY (2020)

Article Chemistry, Multidisciplinary

Total Syntheses of (+)-Aquatolide and Related Humulanolides

Ken-ichi Takao et al.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2019)

Article Chemistry, Multidisciplinary

A Pyridine-Pyridine Cross-Coupling Reaction via Dearomatized Radical Intermediates

J. Luke Koniarczyk et al.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2019)

Review Chemistry, Multidisciplinary

Nonconjugated Hydrocarbons as Rigid-Linear Motifs: Isosteres for Material Sciences and Bioorganic and Medicinal Chemistry

Gemma M. Locke et al.

CHEMISTRY-A EUROPEAN JOURNAL (2019)

Article Chemistry, Multidisciplinary

Pyridine-Catalyzed Radical Borylation of Aryl Halides

Li Zhang et al.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2017)

Article Chemistry, Multidisciplinary

Practical and Asymmetric Reductive Coupling of Isoquinolines Templated by Chiral Diborons

Dongping Chen et al.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2017)

Article Chemistry, Multidisciplinary

Homolytic Cleavage of a B-B Bond by the Cooperative Catalysis of Two Lewis Bases: Computational Design and Experimental Verification

Guoqiang Wang et al.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2016)

Review Chemistry, Multidisciplinary

The electron is a catalyst

Armido Studer et al.

NATURE CHEMISTRY (2014)

Article Chemistry, Organic

Intramolecular Butenolide Allene Photocycloadditions and Ensuing Retro-Ene Reactions of Some Photoadducts

Ginger Lutteke et al.

EUROPEAN JOURNAL OF ORGANIC CHEMISTRY (2011)

Article Chemistry, Multidisciplinary

Pericyclic cascade reactions of (bicyclo[1.1.0]butylmethyl)amines

Peter Wipf et al.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2006)