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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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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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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The current utility and future potential of multiborylated alkanes

Nature Reviews Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: Sept. 26, 2024

Language: Английский

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Electrochemistry-Enabled C-Heteroatom Bond Formation of Alkyl Germanes

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(31), P. 21257 - 21263

Published: July 26, 2024

Because of their robustness and orthogonal reactivity features, alkyl germanes bear significant potential as functional handles for the construction C(sp3)-rich scaffolds, especially in context modular synthetic approaches. However, to date, only radical-based has been accessible from these handles, which limits types possible decorations. Here, we describe first general C(sp3)–heteroatom bond formation (−GeEt3) by leveraging electrochemistry unlock polar reactivity. This approach allowed us couple C(sp3)–GeEt3 with a variety nucleophiles construct ethers, esters, amines, amides, sulfonamides, sulfides, well C–P, C–F, C–C bonds. The compatibility electrochemical strategy C1 motif was also showcased, involving sequential functionalization Cl, Bpin, ultimately GeEt3 via electrochemistry.

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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Pentafluorosulfanoxylation of Hypervalent Chlorines and Bromines for Access to Pentafluoro(biaryloxy)-λ⁶-sulfanes

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

Published: March 11, 2025

The SF5O group has been less explored as a highly fluorinated substituent on an organic framework. In fact, only few SF5O-containing compounds have reported, and the preparation of relied hazardous reagents special apparatuses. Herein we describe safe efficient access to various pentafluoro(aryloxy)-λ6-sulfanes (ArOSF5) through reaction hypervalent λ3-chlor(brom)anes with [Et3MeN]+[OSF5]−. synthetic application potentials ArOSF5 moieties were demonstrated by inertness OSF5 in presence palladium catalysts, alkalis, nucleophiles.

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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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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Light-enabled intramolecular [2 + 2] cycloaddition via photoactivation of simple alkenylboronic esters

Beilstein Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: 21, P. 854 - 863

Published: April 30, 2025

The photoactivation of organic molecules via energy transfer (EnT) catalysis is often limited to conjugated systems that have low-energy triplet excited states, with simple alkenes remaining an intractable challenge. ability address this limitation, using high sensitizers, would represent attractive platform for future reaction design. Here, we disclose the alkenylboronic esters established alkene scrambling as a rapid probe identify suitable catalyst and boron motif. Cyclic voltammetry, UV–vis analysis, control reactions support sensitization, enabling intramolecular [2 + 2] cycloaddition be realized accessing 3D bicyclic fragments containing handle.

Language: Английский

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