α‐Boryl Carbanions: The Influence of Geminal Heteroatoms in C−C Bond Formation

The Chemical Record, Год журнала: 2024, Номер 24(3)

Опубликована: Фев. 2, 2024

Abstract The wide applications of alpha‐boryl carbanions in selective coupling with organohalides, imines/carbonyls and conjugated unsaturated substrates has become an interesting tool for organic synthesis. Strategically, the inclusion heteroatoms, such as Si, S, N, F, Cl, Br I alpha position opens a new venue towards multifunctionalities molecular design. Here, conceptual practical view on powerful carbanions, containing α‐silicoboron, α‐thioboron, α‐haloboron α‐aminoboron is given, well prespective their efficient application electrophilic trapping.

Язык: Английский

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Diverse Synthesis of (Thio)ethers and (Thio)esters Using Halodiborylmethane as a Transformable C₁ Building Block

Organic Letters, Год журнала: 2024, Номер 26(33), С. 7010 - 7014

Опубликована: Авг. 8, 2024

The development of effective strategies to forge C–O and C–S bonds in diverse chemical spaces is considerable interest synthetic organic chemistry. Herein we report a versatile approach for the modular synthesis structurally (thio)ethers (thio)esters via homologative coupling α-halodiborylmethane followed by transformation introduced diborylmethyl group. This method accommodates wide array oxygen- sulfur-containing molecules, including biologically active compounds. initial exhibits broad substrate scope, while subsequent diversification moiety enables access various structural motifs through deborylative alkylation, Zweifel olefination, boron-Wittig reaction. protocol efficiently generates diversely functionalized (thio)esters, expanding toolkit accessing relevant scaffolds.

Язык: Английский

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Anion-Mediated, Stereospecific Synthesis of Secondary and Tertiary Cyclopropylboronates from Chiral Epoxides and gem-Diborylalkanes

Organic Letters, Год журнала: 2023, Номер 25(22), С. 4130 - 4134

Опубликована: Май 25, 2023

We report a transition-metal-free deborylative cyclization approach to synthesize enantioenriched secondary and tertiary cyclopropylboronates using γ-phosphate-containing gem-diborylalkanes derived from chiral epoxides gem-diborylalkanes. Our method enables the synthesis of broad range in good yields with excellent stereospecificity. demonstrate versatility our by performing gram-scale reaction. also show that can be transformed into wide array cyclopropane derivatives stereospecific boron-group transformation.

Язык: Английский

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Palladium-Catalyzed Cross-Coupling of gem-Difluorocyclopropanes with gem-Diborylalkanes for the Synthesis of Boryl-Substituted Fluorinated Alkenes

Organic Letters, Год журнала: 2023, Номер 25(50), С. 9020 - 9024

Опубликована: Дек. 8, 2023

This study presents a novel method for the regioselective coupling of gem-difluorinated cyclopropanes with gem-diborylmethane, utilizing Pd-catalyst system. innovative approach enables synthesis 2-fluoroalkenyl monoboronate scaffolds high Z-selectivity. The resulting products undergo further transformations, including oxidation, Suzuki cross-coupling, and trifluoroborylation, all which are achieved good yields. work introduces valuable synthetic pathway to access important fluorinated compounds various applications in organic chemistry.

Язык: Английский

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Mechanochemical Synthesis of α‐halo Alkylboronic Esters

Advanced Science, Год журнала: 2024, Номер 11(33)

Опубликована: Июль 3, 2024

α-halo alkylboronic esters, acting as ambiphilic synthons, play a pivotal role versatile intermediates in fields like pharmaceutical science and organic chemistry. The sequential transformation of carbon-boron carbon-halogen bonds into broad range carbon-X allows for programmable bond formation, facilitating the incorporation multiple substituents at single position streamlining synthesis complex molecules. Nevertheless, synthetic potential these compounds is constrained by limited reaction patterns. Additionally, conventional methods often necessitate use bulk toxic solvents, exhibit sensitivity to air/moisture, rely on expensive metal catalysts, involve extended times. In this report, ball milling technique introduced that overcomes limitations, enabling external catalyst-free multicomponent coupling aryl diazonium salts, alkenes, simple halides. This approach offers general straightforward method obtaining diverse array thereby paving way extensive utilization synthons fine chemicals.

Язык: Английский

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Selective Formal Carbene Insertion into Carbon‐Boron Bonds of Diboronates byN‐Trisylhydrazones

Angewandte Chemie International Edition, Год журнала: 2022, Номер 62(9)

Опубликована: Дек. 28, 2022

Bisborylalkanes play important roles in organic synthesis as versatile bifunctional reagents. The two boron moieties these compounds can be selectively converted into other functional groups through cross-coupling, oxidation or radical reactions. Thus, the development of efficient methods for synthesizing bisborylalkanes is highly demanded. Herein we report a new strategy to access reaction N-trisylhydrazones with diboronate, which bis(boryl) methane transformed 1,2-bis(boronates) via formal carbene insertion. Since readily derived from corresponding aldehydes, this represents practical 1,2-diboronates broad substrate scope. Mechanistic studies reveal an unusual neighboring group effect 1,1-bis(boronates), accounts observed regioselectivity when unsymmetric 1,1-diboronates are applied.

Язык: Английский

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Construction of α-Halogenated Boronic Esters via Visible Light-Induced C–H Bromination

The Journal of Organic Chemistry, Год журнала: 2023, Номер 88(19), С. 14246 - 14254

Опубликована: Сен. 21, 2023

α-Halogenated boronic esters are versatile building blocks that can be diversified into a wide variety of polyfunctionalized molecules. However, their synthetic potential has been hampered by limited preparation methods. Herein, we report visible light-induced C-H bromination reaction readily available benzyl esters. This method features high yields, mild conditions, simple operation, and good functional group tolerance. The analogous chlorides iodides accessed via Finkelstein reaction. Synthesis halogenated geminal diborons also demonstrated.

Язык: Английский

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Modular Synthesis of Geminal Iododiboron Compounds via Alkylation of Chlorodiborylmethane

Organic Letters, Год журнала: 2024, Номер unknown

Опубликована: Ноя. 22, 2024

α-Halogenated geminal bis(boronates) are emerging as multifunctional building blocks for organic synthesis. Currently, their synthetic utilization is still restricted due to a lack of efficient preparation methods. Herein, we report direct, modular synthesis gem-iododiborylalkanes using alkyl halides and lithiated chlorodiborylmethane reagent. Compared with previously reported methods, this protocol features assembly, high efficiency, good tolerance various functional groups.

Язык: Английский

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Synthesis of 1,4-Diketones from Esters Enabled by a Tetraborylethane Reagent

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Янв. 25, 2025

A modular synthesis method for 1,4-diketones has been developed. Utilizing inexpensive carboxylic acid esters as carbonyl sources and tetraborylethane (TBE) a nucleophilic reagent, one-pot strategy constructing two C-C bonds was established. Notably, this reaction proceeds without the involvement of transition metals exhibits excellent functional group compatibility. diverse array α-substituted were synthesized using various electrophiles capture.

Язык: Английский

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Synthesis of α-Chloroboronic Esters via Photoredox-Catalyzed Chloro-Alkoxycarbonylation of Vinyl Boronic Esters

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Март 9, 2025

α-Chloroboronic esters are a class of stable multifunctional molecules that show unique applications in pharmaceutical science and organic chemistry. Despite their apparent utility, the synthetic methods these compounds remain limited. Herein, novel strategy for efficient synthesis α-chloroboronic is developed via photoredox-catalyzed chloro-alkoxycarbonylation vinyl boronic esters. This features advantages high atom economy, environmental friendliness, excellent functional group compatibility was verified by cross-coupling variety free alcohols, oxalyl chlorides, Control experiments mechanistic studies indicate alkoxycarbonyl radical α-boryl carbocation key intermediates this transformation.

Язык: Английский

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