Cu-Catalyzed Diastereo- and Enantioselective Synthesis of Borylated Cyclopropanes with Three Contiguous Stereocenters

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

Published: Jan. 17, 2025

Direct synthesis of enantioenriched scaffolds with multiple adjacent stereocenters remains an important yet challenging task. Herein, we describe a highly diastereo- and enantioselective Cu-catalyzed alkylboration cyclopropenes, less reactive alkyl iodides as electrophiles, for the efficient tetra-substituted borylated cyclopropanes bearing three consecutive stereocenters. This protocol features mild conditions, broad substrate scope, good functional group tolerance, affording array chiral in to high yields excellent enantioselectivities. Detailed mechanistic experiments kinetic studies were conducted elucidate reaction pathway rate-determining step reaction. DFT calculations revealed that π···π stacking interaction between phenyl groups on phosphorus ligand, along smaller distortion CuL-Bpin part, contributed The synthetic utility was showcased by facile some valuable centers.

Language: Английский

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Diborodichloromethane as Versatile Reagent for Chemodivergent Synthesis of gem‐Diborylalkanes

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 63(3)

Published: Dec. 8, 2023

Abstract The development of boron reagents is crucial for synthetic chemistry. Herein, we present a scalable and practical synthesis diborodichloromethane (DBDCM) through the reaction trichloromethyllithium with bis(pinacolato)diboron (B 2 pin ). resulting DBDCM reagent serves as basic unit construction various structurally diverse gem ‐diborylalkanes controllable C−Cl functionalizations. Moreover, have developed consecutive tetra‐functionalizations tertiary quaternary carbon containing molecules. use isotopically enriched 13 C‐chloroform 10 B enables C‐DBDCM B‐DBDCM reagents, which are beneficial convenient carbon‐13 boron‐10

Language: Английский

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Palladium‐Catalyzed Cascade Heck Coupling and Allylboration of Iododiboron Compounds via Diboryl Radicals

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(18)

Published: March 6, 2024

Geminal bis(boronates) are versatile synthetic building blocks in organic chemistry. The fact that they predominantly serve as nucleophiles the previous reports, however, has restrained their potential. Herein we disclose ambiphilic reactivity of α-halogenated geminal bis(boronates), which first catalytic utilization was accomplished by merging a formal Heck cross-coupling with highly diastereoselective allylboration aldehydes or imines, providing new avenue for rapid assembly polyfunctionalized boron-containing compounds. We demonstrated this cascade reaction is efficient and compatible various functional groups, wide range heterocycles. In contrast to classical Pd(0/II) scenario, mechanistic experiments DFT calculations have provided strong evidence cycle involving Pd(I)/diboryl carbon radical intermediates.

Language: Английский

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Catalytic Reductive Aza-Boron-Wittig Reaction

ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 3741 - 3750

Published: Feb. 17, 2025

Language: Английский

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Facile Synthesis of Housanes by an Unexpected Strategy

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

Published: Feb. 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.

Language: Английский

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A General Method to Access Sterically Encumbered Geminal Bis(boronates) via Formal Umpolung Transformation of Terminal Diboron Compounds

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 63(4)

Published: Dec. 8, 2023

Abstract General methods for the preparation of geminal bis(boronates) are great interest due to their widespread applications in organic synthesis. While terminal gem ‐diboron compounds readily accessible, construction sterically encumbered, internal analogues has remained a prominent challenge. Herein, we report formal umpolung strategy access these valuable building blocks. The available 1,1‐diborylalkanes were first converted into corresponding α‐halogenated derivatives, which then serve as electrophilic components, undergoing substitution with diverse array nucleophiles form series C−C, C−O, C−S, and C−N bonds. This protocol features good tolerance steric hindrance wide variety functional groups heterocycles. Notably, this can also be extended synthesis diaryl compounds, therefore providing general approach various types bis(boronates).

Language: Английский

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Boron Ylide Enables Stereoselective Construction of gem‐Diborylcyclopropanes

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: unknown

Published: Sept. 20, 2024

Abstract The stereoselective cyclopropanation of olefins with “boron ylide” is disclosed for the first time, providing a modular strategy synthesis stereospecific diboryl‐functionalized cyclopropanes. chiral gem ‐diborylcyclopropanes are synthesized excellent enantioselectivity aid auxiliary. Based on powerful transformable ability boryl group, those challenging multi‐quaternary carbon centers in cyclopropane units have been facilely constructed stereoselectivity. Control experiments indicate that groups necessary both chemoselectivity and stereoselectivity control.

Language: Английский

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Silver-catalyzed direct conversion of epoxides into cyclopropanes using N-triftosylhydrazones

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: March 2, 2024

Abstract Epoxides, as a prominent small ring O -heterocyclic and the privileged pharmacophores for medicinal chemistry, have recently represented an ideal substrate development of single-atom replacements. The previous -to- C replacement strategy epoxides to date typically requires high temperatures achieve low yields lacks range functional group tolerance, so achieving this oxygen-carbon exchange remains formidable challenge. Here, we report silver-catalyzed direct conversion into trifluoromethylcyclopropanes in single step using trifluoromethyl N -triftosylhydrazones carbene precursors, thereby via tandem deoxygenation/[2 + 1] cycloaddition. reaction shows broad tolerance groups, allowing routine cheletropic olefin synthesis net reaction. utility method is further showcased with late-stage diversification derived from bioactive natural products drugs. Mechanistic experiments DFT calculations elucidate mechanism origin chemo- stereoselectivity.

Language: Английский

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Advances in the Synthesis of Cyclopropylamines

Chemical Reviews, Journal Year: 2025, Volume and Issue: unknown

Published: March 6, 2025

Cyclopropylamines are an important subclass of substituted cyclopropanes that combine the unique electronic and steric properties with presence a donor nitrogen atom. In addition to their in diverse array biologically active compounds, cyclopropylamines utilized as synthetic intermediates, particularly ring-opening or cycloaddition reactions. Consequently, synthesis these compounds has constituted significant research topic, evidenced by abundant published methods. widely used Curtius rearrangement, classical cyclopropanation methods have been adapted integrate function (Simmons-Smith reaction, metal-catalyzed reaction diazo on olefins, Michael-initiated ring-closure reactions) advances enantioselective synthesis. More recently, specific developed for preparation aminocyclopropane moiety (Kulinkovich reactions applied amides nitriles, cyclopropenes, involving C-H functionalization, ...). The topic this review is present different cyclopropylamine derivatives, aim covering methodological best possible, highlighting scope, stereochemical aspects future trends.

Language: Английский

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Synthesis of α-Substituted Cyclic Boronates via Titanium-Catalyzed Cyclization of Vinyl Boronates with Dihaloalkanes

Chemical Science, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

A titanium-catalyzed reductive cyclization of vinyl boronates with gem -dihaloalkanes is developed. α-Substituted cyclic that are otherwise difficult to access, such as those heteroatom-containing rings, readily obtained.

Language: Английский

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