Palladium-catalyzed decarboxylative (4 + 3) cycloadditions of bicyclobutanes with 2-alkylidenetrimethylene carbonates for the synthesis of 2-oxabicyclo[4.1.1]octanes

Chemical Science, Год журнала: 2024, Номер 15(34), С. 13942 - 13948

Опубликована: Янв. 1, 2024

While cycloaddition reactions of bicyclobutanes (BCBs) have emerged as a potent method for synthesizing (hetero-)bicyclo[

Язык: Английский

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Zinc‐Catalyzed Enantioselective Formal (3+2) Cycloadditions of Bicyclobutanes with Imines: Catalytic Asymmetric Synthesis of Azabicyclo[2.1.1]hexanes

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(48)

Опубликована: Сен. 2, 2024

Abstract The cycloaddition reaction involving bicyclo[1.1.0]butanes (BCBs) offers a versatile and efficient synthetic platform for producing C(sp 3 )‐rich rigid bridged ring scaffolds, which act as phenyl bioisosteres. However, there is scarcity of catalytic asymmetric cycloadditions BCBs to fulfill the need enantioenriched saturated bicycles in drug design development. In this study, an synthesis valuable azabicyclo[2.1.1]hexanes (aza‐BCHs) by enantioselective zinc‐catalyzed (3+2) with imines reported. proceeds effectively novel type BCB that incorporates 2‐acyl imidazole group diverse array alkynyl‐ aryl‐substituted imines. target aza‐BCHs, consist α‐chiral amine fragments two quaternary carbon centers, are efficiently synthesized up 94 % 96.5:3.5 er under mild conditions. Experimental computational studies reveal follows concerted nucleophilic ring‐opening mechanism This distinct from previous on Lewis acid‐catalyzed BCBs.

Язык: Английский

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Divergent Synthesis of Sulfur‐Containing Bridged Cyclobutanes by Lewis Acid Catalyzed Formal Cycloadditions of Pyridinium 1,4‐Zwitterionic Thiolates and Bicyclobutanes

Angewandte Chemie International Edition, Год журнала: 2024, Номер unknown

Опубликована: Май 31, 2024

Bridged cyclobutanes and sulfur heterocycles are currently under intense investigation as building blocks for pharmaceutical drug design. Two formal cycloaddition modes involving bicyclobutanes (BCBs) pyridinium 1,4-zwitterionic thiolate derivatives were described to rapidly expand the chemical space of sulfur-containing bridged cyclobutanes. By using Ni(ClO

Язык: Английский

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Facile access to bicyclo[2.1.1]hexanes by Lewis acid-catalyzed formal cycloaddition between silyl enol ethers and bicyclo[1.1.0]butanes

Nature Communications, Год журнала: 2024, Номер 15(1)

Опубликована: Июль 20, 2024

Abstract Saturated three-dimensional carbocycles have gained increasing prominence in synthetic and medicinal chemistry. In particular, bicyclo[2.1.1]hexanes (BCHs) been identified as the molecular replacement for benzenes. Here, we present facile access to a variety of BCHs via stepwise two-electron formal (3 + 2) cycloaddition between silyl enol ethers bicyclo[1.1.0]butanes (BCBs) under Lewis acid catalysis. The reaction features wide functional group tolerance ethers, allowing efficient construction two vicinal quaternary carbon centers silyl-protected tertiary alcohol unit streamlined fashion. Interestingly, with conjugated dienol can provide bicyclo[4.1.1]octanes (BCOs) equipped that facilitate further transformation. utilities this methodology are demonstrated by late-stage modification natural products, transformations units on bicyclo[2.1.1]hexane frameworks, derivatization bicyclo[4.1.1]octanes, delivering functionalized bicycles traditionally inaccessible.

Язык: Английский

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Facile Synthesis of Housanes by an Unexpected Strategy

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

Опубликована: Фев. 17, 2025

Rigid bicyclic hydrocarbons have emerged as important building blocks in the drug discovery industry. Despite progress this general area, bicyclo[2.1.0]pentanes (housanes) are an understudied class of molecules. Herein we report unconventional synthesis borylated housanes. Our method features a broad scope and high diastereoselectivities versatile intermediates. The route involves strain-release diboration bicyclo[1.1.0]butane intramolecular deborylative alkylation. versatility bridgehead boronic ester was demonstrated several functionalizations. Lastly, mechanism reaction investigated, unusual stereospecific diastereoselective ring expansion uncovered.

Язык: Английский

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

Chem, Год журнала: 2024, Номер unknown

Опубликована: Сен. 1, 2024

Язык: Английский

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PolyBorylated Alkenes as Energy‐Transfer Reactive Groups: Access to Multi‐Borylated Cyclobutanes Combined with Hydrogen Atom Transfer Event

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(25)

Опубликована: Апрель 11, 2024

Abstract While polyborylated alkenes are being recognized for their elevated status as highly valuable reagents in modern organic synthesis, allowing efficient access to a diverse array of transformations, including the formation C−C and C‐heteroatom bonds, potential energy‐transfer reactive groups has remained unexplored. Yet, this holds key generating elusive biradical species, which can be captured by olefins, thereby leading construction new highly‐borylated scaffolds. Herein, we report designed strategy photosensitized [2+2]‐cycloadditions poly‐borylated with various olefins enabling regioselective synthesis cyclobutane motifs, 1,1‐di‐, 1,1,2‐tri‐, 1,1,2,2‐tetra‐borylated cyclobutanes. In fact, these compounds belong family that presently lacks synthetic pathways. Interestingly, when α‐methylstyrene was used, reaction involves an interesting 1,5‐hydrogen atom transfer (HAT). Mechanistic deuterium‐labeling studies have provided insight into outcome process. addition, cyclobutanes then demonstrated useful selective oxidation processes resulting cyclobutanones γ‐lactones.

Язык: Английский

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Enantioselective photocatalytic synthesis of bicyclo[2.1.1]hexanes as ortho-disubstituted benzene bioisosteres with improved biological activity

Nature Chemistry, Год журнала: 2025, Номер unknown

Опубликована: Фев. 25, 2025

Язык: 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, Год журнала: 2024, Номер unknown

Опубликована: Июль 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

Язык: Английский

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Norrish-Yang-type cyclopropanation via functional group migration with photosensitizer at ppb loading

Chem Catalysis, Год журнала: 2024, Номер unknown, С. 101099 - 101099

Опубликована: Сен. 1, 2024

Язык: Английский

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