Palladium‐Catalyzed Cascade Heck Coupling and Allylboration of Iododiboron Compounds via Diboryl Radicals DOI
Wei Yi, Xiaoyu Xie, Jiabin Liu

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(18)

Published: March 6, 2024

Abstract Geminal bis(boronates) are versatile synthetic building blocks in organic chemistry. The fact that they predominantly serve as nucleophiles the previous reports, however, has restrained their potential. Herein we disclose ambiphilic reactivity of α‐halogenated geminal bis(boronates), which first catalytic utilization was accomplished by merging a formal Heck cross‐coupling with highly diastereoselective allylboration aldehydes or imines, providing new avenue for rapid assembly polyfunctionalized boron‐containing compounds. We demonstrated this cascade reaction is efficient and compatible various functional groups, wide range heterocycles. In contrast to classical Pd(0/II) scenario, mechanistic experiments DFT calculations have provided strong evidence cycle involving Pd(I)/diboryl carbon radical intermediates.

Language: Английский

Facile Synthesis of Housanes by an Unexpected Strategy DOI
Yanyao Liu,

Somanea Tranin,

Yu‐Che Chang

et al.

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 17, 2025

Rigid bicyclic hydrocarbons have emerged as important building blocks in the drug discovery industry. Despite progress this general area, bicyclo[2.1.0]pentanes (housanes) are an understudied class of molecules. Herein we report unconventional synthesis borylated housanes. Our method features a broad scope and high diastereoselectivities versatile intermediates. The route involves strain-release diboration bicyclo[1.1.0]butane intramolecular deborylative alkylation. versatility bridgehead boronic ester was demonstrated several functionalizations. Lastly, mechanism reaction investigated, unusual stereospecific diastereoselective ring expansion uncovered.

Language: Английский

Citations

2
Palladium‐Catalyzed Cascade Heck Coupling and Allylboration of Iododiboron Compounds via Diboryl Radicals DOI
Wei Yi, Xiaoyu Xie, Jiabin Liu

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(18)

Published: March 6, 2024

Geminal bis(boronates) are versatile synthetic building blocks in organic chemistry. The fact that they predominantly serve as nucleophiles the previous reports, however, has restrained their potential. Herein we disclose ambiphilic reactivity of α-halogenated geminal bis(boronates), which first catalytic utilization was accomplished by merging a formal Heck cross-coupling with highly diastereoselective allylboration aldehydes or imines, providing new avenue for rapid assembly polyfunctionalized boron-containing compounds. We demonstrated this cascade reaction is efficient and compatible various functional groups, wide range heterocycles. In contrast to classical Pd(0/II) scenario, mechanistic experiments DFT calculations have provided strong evidence cycle involving Pd(I)/diboryl carbon radical intermediates.

Language: Английский

Citations

14
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
Synthesis of 1,4-Diketones from Esters Enabled by a Tetraborylethane Reagent DOI
Miaomiao Wu,

Tongchang Fang,

Liangxuan Xu

et al.

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

Citations

0
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
Organocatalytic Asymmetric Allylic Benzylborylation via Fluoride-Assisted Catalytic Generation of α-Boryl Carbanionic Intermediates DOI Creative Commons
Jordi Duran, Paula Rodríguez,

W.A.H. Vermeer

et al.

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

Published: Sept. 20, 2024

Herein we describe the organocatalytic asymmetric allylic benzylborylation of allyl fluorides with α-silyl benzylboronic esters. The catalytic protocol leverages singular features fluoride as an unconventional leaving group, enabling generation reactive α-boryl carbanion species through desilylative activation. It allows construction a wide set homoallylic benzylated organoboronates bearing two contiguous stereocenters. chiral boronate installed in products serves synthetic lynchpin to construct complex chemical architectures stereospecific manner.

Language: Английский

Citations

0
Palladium‐Catalyzed Cascade Heck Coupling and Allylboration of Iododiboron Compounds via Diboryl Radicals DOI
Wei Yi, Xiaoyu Xie, Jiabin Liu

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(18)

Published: March 6, 2024

Abstract Geminal bis(boronates) are versatile synthetic building blocks in organic chemistry. The fact that they predominantly serve as nucleophiles the previous reports, however, has restrained their potential. Herein we disclose ambiphilic reactivity of α‐halogenated geminal bis(boronates), which first catalytic utilization was accomplished by merging a formal Heck cross‐coupling with highly diastereoselective allylboration aldehydes or imines, providing new avenue for rapid assembly polyfunctionalized boron‐containing compounds. We demonstrated this cascade reaction is efficient and compatible various functional groups, wide range heterocycles. In contrast to classical Pd(0/II) scenario, mechanistic experiments DFT calculations have provided strong evidence cycle involving Pd(I)/diboryl carbon radical intermediates.

Language: Английский

Citations

0