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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Photoinduced Assembly of Diverse Homoallylic Boronates from gem-Diborons

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Март 7, 2025

In comparison to alkyl monoboron or 1,2-diboron, which can generate radicals via tetracoordinate boron species under photocatalytic conditions, the participation of gem-diborons as substrates in such reactions remains be developed. Herein, we report a method utilizing starting materials α-boryl radicals, then react with various olefins, successfully and efficiently constructing diverse range high-value homoallylic boronates; meanwhile, gem-difluorohomoallylic skeletons could also smoothly obtained. This transformation demonstrates broad substrate scope excellent tolerance toward functional groups, enhancing utility gem-diboron precursors for C-C bond construction production valuable products.

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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Synthesis of gem-Diborylcyclopropyl Ketones via Conjugate Addition of Chlorodiborylmethane to α,β-Unsaturated Ketones

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Апрель 3, 2025

The carbanion derived from chlorodiborylmethane can act as a soft nucleophile, while the halogen substituent subsequently function leaving group. Taking advantage of this feature, we herein have developed an efficient synthesis gem-diborylcyclopropyl ketones diverse range enone substrates. We also demonstrated synthetic utility protocol by leveraging highly transformable nature cyclopropyl moiety and C-B bonds.

Язык: Английский

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Synthesis of γ-Iodo-allylic Diboronic Esters via Atom Transfer Radical Addition of (Diborylmethyl)iodide to Alkynes

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Апрель 11, 2025

Herein, we disclose a manganese-catalyzed approach that enables the direct iododiborylcarbofunctionalization of alkynes with (diboronmethyl)iodide under mild conditions. This grants access to range structurally unique and synthetically useful γ-iodine-substituted gem-bis(boronate)s, which have hitherto been inaccessible. atom-economical strategy displays excellent functional-group tolerance, encompasses wide applicable substrates, demonstrates high Z:E selectivity (up 96:4).

Язык: Английский

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Diastereoselective Synthesis of Boryl-Substituted Vinylcyclopropanes via Deborylative Cyclization of Geminal Diboron Compounds

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Апрель 14, 2025

Herein we report a diastereoselective synthesis of boryl-substituted vinylcyclopropanes, class highly valuable synthetic building blocks, via deborylative cyclization geminal diboron compounds. The method exhibits broad functional group tolerance and accommodates diverse alkyl aryl α-substituents. diastereoselectivity is primarily governed by the α-substituent (alkyl vs aryl), while olefin geometry in side chain has secondary influence. Mechanistic studies indicated distinct pathways: concerted process for substrates carbanion intermediate derivatives. Synthetic utility products was also demonstrated.

Язык: Английский

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Modular Synthesis of Chiral 1,3-Diboronates with Differentiable Boryl Groups via Cu-Catalyzed Borylalkylation of Styrenes

ACS Catalysis, Год журнала: 2025, Номер unknown, С. 8913 - 8924

Опубликована: Май 12, 2025

Язык: Английский

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Boryl Radical Mediated Hydro(gem-diboryl)alkylation of Alkenes with Sterically Hindered NHC Boranes

Organic Letters, Год журнала: 2024, Номер unknown

Опубликована: Дек. 9, 2024

NHC boryl radical mediated halogen atom transfer (XAT) is useful in organic synthesis. Yet, most of the reaction ends only with reducing to hydrogen, that is, C-X C-H. This especially dominant for electron-deficient alkyl halides, where formed electrophilic reacts rapidly boranes. Herein, by employing a sterically hindered borane as precursor (IPr·BH

Язык: Английский

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