Merging Ketyl Radical Chemistry and Allylboration via Strain Release: One-Pot Multicomponent Access to Sterically Congested Ketone-Functionalized Organoborons

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: March 17, 2025

Ketyl radical-mediated ring opening and [2σ+2π] cycloaddition of cyclopropyl ketones (CPKs) with alkynes typically require activation by alkyl, aryl, or carbonyl groups yielding cyclopentenes having one two non-adjacent stereocenters. We developed a one-pot multicomponent reaction diboryl-activated CPKs aldehydes that merges ketyl radical chemistry allylboration. This method enabled highly diastereoselective access to densely functionalized featuring homoallylic alcohol, ketone, alkenyl boronate motifs on adjacent quaternary, tertiary, secondary stereogenic centers. Additionally, diboryl also allowed the synthesis rare ketone-functionalized γ,γ-disubstituted allylic diborons.

Language: Английский

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Construction of 1,3‐Diboryl Allenes from gem‐Iododiboron Compounds via Intermolecular Boryl Group Transfer^†

Chinese Journal of Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 23, 2025

Comprehensive Summary Allenylboronates are valuable synthetic building blocks and have garnered significant interest. However, their 1,3‐diboyl substituted analogs not been reported. Herein, we disclosed a novel method for creating allenes from gem ‐iododiboron compounds alkynyl Grignard reagents. The starting materials initially converted into the corresponding propargylic ‐bis(boronates), which then undergo an intermolecular boryl group transfer to afford allenes, as confirmed by mechanistic studies. This features good tolerance steric hindrance is compatible with wide variety of functional groups.

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

Organic Letters, Journal Year: 2024, Volume and Issue: 26(33), P. 7010 - 7014

Published: Aug. 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.

Language: Английский

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

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 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.

Language: Английский

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

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: April 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).

Language: Английский

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Strain-release enables access to carbonyl conjugated allylic diborons and alkenyl boronates having multiple contiguous stereocenters in a one-pot process

Chemical Science, Journal Year: 2024, Volume and Issue: unknown

Published: Jan. 1, 2024

A strain-release promoted cycloaddition opens-up access to carbonyl conjugated allylic diborons and borylated homoallylic alcohols, β-spiro lactones γ-butyrolactones having adjacent quaternary, tertiary secondary stereocenters.

Language: Английский

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Photoinduced Assembly of Diverse Homoallylic Boronates from gem-Diborons

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: March 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.

Language: Английский

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

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: April 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.

Language: Английский

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Modular Synthesis of Geminal Iododiboron Compounds via Alkylation of Chlorodiborylmethane

Organic Letters, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 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.

Language: Английский

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