Stereo- and Enantioselective Syntheses of 1,2-Oxaborinan-3-enes and δ-Boryl-Substituted Homoallylic Alcohols DOI Creative Commons
Zheye Zhang, Ming Chen

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

Published: Nov. 19, 2024

Stereo- and enantioselective syntheses of 1,2-oxaborinan-3-enes δ-boryl-substituted homoallylic alcohols are reported. We developed a practical approach to synthesize α-boryl-substituted allylboronate. This reagent was utilized generate α,α-disubstituted allylboronates, such reagents cannot be accessed via the Pd-catalyzed alkene isomerization approach. Chiral Brønsted-acid-catalyzed aldehyde addition with these gave excellent stereo- enantioselectivities. Lewis-acid-catalyzed also worked well, affording high stereoselectivities. The variant reaction achieved chiral

Language: Английский

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
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 gem-Diborylcyclopropyl Ketones via Conjugate Addition of Chlorodiborylmethane to α,β-Unsaturated Ketones DOI
Shuang Xu,

Peng‐Fei Ning,

Yi Wei

et al.

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

Citations

0
Modular Synthesis of Geminal Iododiboron Compounds via Alkylation of Chlorodiborylmethane DOI
Yifei Yang,

Peng‐Fei Ning,

Bo Zhang

et al.

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

Citations

3
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
Boryl Radical Mediated Hydro(gem-diboryl)alkylation of Alkenes with Sterically Hindered NHC Boranes DOI

Ruizeng Zhang,

Hao Zhang,

Pan Xu

et al.

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

Published: Dec. 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

Language: Английский

Citations

1
Stereo- and Enantioselective Syntheses of 1,2-Oxaborinan-3-enes and δ-Boryl-Substituted Homoallylic Alcohols DOI Creative Commons
Zheye Zhang, Ming Chen

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

Published: Nov. 19, 2024

Stereo- and enantioselective syntheses of 1,2-oxaborinan-3-enes δ-boryl-substituted homoallylic alcohols are reported. We developed a practical approach to synthesize α-boryl-substituted allylboronate. This reagent was utilized generate α,α-disubstituted allylboronates, such reagents cannot be accessed via the Pd-catalyzed alkene isomerization approach. Chiral Brønsted-acid-catalyzed aldehyde addition with these gave excellent stereo- enantioselectivities. Lewis-acid-catalyzed also worked well, affording high stereoselectivities. The variant reaction achieved chiral

Language: Английский

Citations

0