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

Peng‐Fei Ning,

Yi Wei, Xinyi Chen

et al.

Angewandte Chemie, Journal Year: 2023, Volume and Issue: 136(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

Diborodichloromethane as Versatile Reagent for Chemodivergent Synthesis of gem‐Diborylalkanes DOI

Tongchang Fang,

Liwei Wang, Miaomiao Wu

et al.

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

Citations

25
Construction of 1,3‐Diboryl Allenes from gem‐Iododiboron Compounds via Intermolecular Boryl Group Transfer† DOI Open Access
Ming Li, Yi Wei, Du Chen

et al.

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

Citations

1
A General Method to Access Sterically Encumbered Geminal Bis(boronates) via Formal Umpolung Transformation of Terminal Diboron Compounds DOI Open Access

Peng‐Fei Ning,

Yi Wei, Xinyi Chen

et al.

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

Citations

21
Boron Ylide Enables Stereoselective Construction of gem‐Diborylcyclopropanes DOI

Tongchang Fang,

Peng Zhang,

Chao Liu

et al.

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

Citations

8
Recent progress in visible light‐driven halogenation: Chlorination, bromination, and iodination DOI

Anh Thu Nguyen,

Houng Kang, Truong Giang Luu

et al.

Bulletin of the Korean Chemical Society, Journal Year: 2024, Volume and Issue: 45(9), P. 738 - 758

Published: Sept. 1, 2024

Abstract Halogenation is one of the most important transformations in organic synthesis. Halogenated compounds are employed many reactions to prepare useful molecules. Many methods have been developed introduce halogens into different compounds. Visible light‐mediated efficient, low‐toxic, and mild‐condition applied for various chemistry transformations. Remarkably, there has an increasing development application visible light‐induced halogenation recent years. Herein, we present a comprehensive summary including chlorination, bromination, iodination under light irradiation since 2020.

Language: Английский

Citations

5
Synthesis of α-Chloroboronic Esters via Photoredox-Catalyzed Chloro-Alkoxycarbonylation of Vinyl Boronic Esters DOI
Wen‐Duo Li, Nana Wei, Nan Feng

et al.

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

Published: March 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.

Language: Английский

Citations

0
Efficient Synthesis of α-Haloboronic Esters via Cu-Catalyzed Atom Transfer Radical Addition DOI

Tam D. Ho,

Byung‐Joo Lee,

Catherine Tan

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(50), P. 27230 - 27235

Published: Dec. 6, 2023

The synthesis of α-haloboronic esters via atom transfer radical addition (ATRA) is constrained due to its limited range compatible substrates or the need manipulate olefin coupling partners. Herein, we present a novel approach for their Cu-catalyzed ATRA vinyl boronic esters. catalyst proposed mediate traditionally inefficient halogen α-boryl intermediate, thus significantly expanding participating relative established methods. forty-eight examples illustrate that wide precursors, including primary, secondary, and tertiary alkyl halides, readily add across both unsubstituted α-substituted pinacol Further, one-pot, two-step protocol presented direct access an array α-functionalized products. Finally, synthetic utility this methodology demonstrated in ixazomib analogue.

Language: Английский

Citations

8
Boron Ylide Enables Stereoselective Construction of gem‐Diborylcyclopropanes DOI

Tongchang Fang,

Peng Zhang,

Chao Liu

et al.

Angewandte Chemie, 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

Citations

1
Diastereoselective Homocoupling of Benzylic C(sp3)–H Bonds Enabled by Halogen Transfer DOI
Xirong Liu, Xin An, Xue Zhao

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(43), P. 9257 - 9262

Published: Oct. 18, 2024

A transition-metal- and harsh-oxidant-free strategy for diastereoselective homocoupling of benzylic α-boryl carbanions has been developed. Central to this methodology is the ability halogen transfer reagent seamlessly integrate halogenation substitution within a compatible process. Additionally, also applicable diarylmethanes alkylheteroarenes. Substrates bearing oxidatively sensitive functional groups were well-tolerated. Preliminary studies suggest that hydrogen bond between two boryl contributes high diastereoselectivities.

Language: Английский

Citations

0
Diborodichloromethane as Versatile Reagent for Chemodivergent Synthesis of gem‐Diborylalkanes DOI

Tongchang Fang,

Liwei Wang, Miaomiao Wu

et al.

Angewandte Chemie, Journal Year: 2023, Volume and Issue: 136(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

Citations

0