Desymmetrization of Diboron(4) by a Trifluorination B-Masking Strategy: Practical Synthesis of Unsymmetrical Diboron Species DOI Creative Commons
Nadim Eghbarieh, Ahmad Masarwa

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(16), P. 11753 - 11760

Published: Aug. 1, 2024

Herein, we report a straightforward practical and simple method for efficiently synthesizing BF

Language: Английский

PolyBorylated Alkenes as Energy‐Transfer Reactive Groups: Access to Multi‐Borylated Cyclobutanes Combined with Hydrogen Atom Transfer Event DOI Creative Commons
Nicole Hanania, Nadim Eghbarieh, Ahmad Masarwa

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(25)

Published: April 11, 2024

Abstract While polyborylated alkenes are being recognized for their elevated status as highly valuable reagents in modern organic synthesis, allowing efficient access to a diverse array of transformations, including the formation C−C and C‐heteroatom bonds, potential energy‐transfer reactive groups has remained unexplored. Yet, this holds key generating elusive biradical species, which can be captured by olefins, thereby leading construction new highly‐borylated scaffolds. Herein, we report designed strategy photosensitized [2+2]‐cycloadditions poly‐borylated with various olefins enabling regioselective synthesis cyclobutane motifs, 1,1‐di‐, 1,1,2‐tri‐, 1,1,2,2‐tetra‐borylated cyclobutanes. In fact, these compounds belong family that presently lacks synthetic pathways. Interestingly, when α‐methylstyrene was used, reaction involves an interesting 1,5‐hydrogen atom transfer (HAT). Mechanistic deuterium‐labeling studies have provided insight into outcome process. addition, cyclobutanes then demonstrated useful selective oxidation processes resulting cyclobutanones γ‐lactones.

Language: Английский

Citations

11
Enantioselective Suzuki cross-coupling of 1,2-diboryl cyclopropanes DOI Creative Commons
J. de Pascual Teresa, Marina Velado, Roberto Fernández de la Pradilla

et al.

Chemical Science, Journal Year: 2023, Volume and Issue: 14(6), P. 1575 - 1581

Published: Jan. 1, 2023

Herein, we describe the catalytic enantioselective cross-coupling of 1,2-bisboronic esters. Prior work on group specific cross coupling is limited to use geminal bis-boronates. This desymmetrization provides a novel approach prepare enantioenriched cyclopropyl boronates with three contiguous stereocenters, that could be further derivatized through selective functionalization carbon-boron bond. Our results suggest transmetallation, which enantiodetermining step, takes place retention stereochemistry at carbon.

Language: Английский

Citations

18
Stereodefined polymetalloid alkenes synthesis via stereoselective boron-masking of polyborylated alkenes DOI Creative Commons
Nadim Eghbarieh, Nicole Hanania, Ahmad Masarwa

et al.

Nature Communications, Journal Year: 2023, Volume and Issue: 14(1)

Published: April 11, 2023

Polyborylated-alkenes are valuable polymetalloid reagents in modern organic synthesis, providing access to a wide array of transformations, including the construction multiple C-C and C-heteroatom bonds. However, because they contain similar boryl groups, many times their transformation faces main challenge controlling chemo-, regio- stereoselectivity. One way overcome these limitations is by installing different boron groups that can provide an opportunity tune reactivity toward better Yet, preparation polyborylated-alkenes containing has been rare. Herein we report concise, highly site-selective, stereoselective boron-masking strategies polyborylated alkenes. This achieved designed trifluorination MIDA-ation reactions readily available starting Additionally, trifluoroborylated-alkenes undergo stereospecific interconversion Bdan-alkenes. These transition-metal free general efficient method for conversion alkenes 1,1-di-, 1,2-di-, 1,1,2-tris-(borylated) BF

Language: Английский

Citations

18
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
Photoredox‐Mediated Deoxygenative Radical Additions of Aromatic Acids to Vinyl Boronic Esters and gem‐Diborylalkenes** DOI Creative Commons
Anugula Nagaraju,

Tamer Saiaede,

Nadim Eghbarieh

et al.

Chemistry - A European Journal, Journal Year: 2022, Volume and Issue: 29(3)

Published: Oct. 12, 2022

A new method to access β-keto-gem-diborylalkanes, by direct deoxygenative radical addition of aromatic carboxylic acids gem-dibortlalkenes, is described. The reaction proceeds under mild photoredox catalysis and involves the photochemical C-O bond activation in presence PPh

Language: Английский

Citations

22
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
Diastereoselective Synthesis of Boryl-Substituted Vinylcyclopropanes via Deborylative Cyclization of Geminal Diboron Compounds DOI

Heng-Yu Gu,

Xinyi Chen, Yifei Yang

et al.

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

Published: April 14, 2025

Herein we report a diastereoselective synthesis of boryl-substituted vinylcyclopropanes, class highly valuable synthetic building blocks, via deborylative cyclization geminal diboron compounds. The method exhibits broad functional group tolerance and accommodates diverse alkyl aryl α-substituents. diastereoselectivity is primarily governed by the α-substituent (alkyl vs aryl), while olefin geometry in side chain has secondary influence. Mechanistic studies indicated distinct pathways: concerted process for substrates carbanion intermediate derivatives. Synthetic utility products was also demonstrated.

Language: Английский

Citations

0
Borylated strain rings synthesis via photorearrangements enabled by energy transfer catalysis DOI Creative Commons
Shu-sheng Chen, Yu Zheng,

Zhi-Xi Xing

et al.

Nature Communications, Journal Year: 2025, Volume and Issue: 16(1)

Published: April 19, 2025

Language: Английский

Citations

0
A Stereodivergent Approach to the Synthesis of gem‐Diborylcyclopropanes DOI Creative Commons
Nicole Hanania, Molhm Nassir, Nadim Eghbarieh

et al.

Chemistry - A European Journal, Journal Year: 2022, Volume and Issue: 28(72)

Published: Sept. 26, 2022

We report a designed stereodivergent strategy for the synthesis of gem-diborylcyclopropanes. The reaction provides highly modular approach to prepare cyclopropane ring variants bearing gem-(Bpin,Bpin), gem-(Bpin,Bdan), and gem-(Bpin,BF3 K), with outstanding levels stereocontrol. This was achieved by diastereoselective Pd-catalyzed cyclopropanation reactions gem-diborylalkenes α-diazoarylacetates α-diazoaryl-trifluoromethyl. key success this general protocol trifluorination gem-diborylcyclopropanes, followed stereospecific interconversion trifluoroborate salts into Bdan group.

Language: Английский

Citations

14
PolyBorylated Alkenes as Energy‐Transfer Reactive Groups: Access to Multi‐Borylated Cyclobutanes Combined with Hydrogen Atom Transfer Event DOI Creative Commons
Nicole Hanania, Nadim Eghbarieh, Ahmad Masarwa

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(25)

Published: April 11, 2024

Abstract While polyborylated alkenes are being recognized for their elevated status as highly valuable reagents in modern organic synthesis, allowing efficient access to a diverse array of transformations, including the formation C−C and C‐heteroatom bonds, potential energy‐transfer reactive groups has remained unexplored. Yet, this holds key generating elusive biradical species, which can be captured by olefins, thereby leading construction new highly‐borylated scaffolds. Herein, we report designed strategy photosensitized [2+2]‐cycloadditions poly‐borylated with various olefins enabling regioselective synthesis cyclobutane motifs, 1,1‐di‐, 1,1,2‐tri‐, 1,1,2,2‐tetra‐borylated cyclobutanes. In fact, these compounds belong family that presently lacks synthetic pathways. Interestingly, when α‐methylstyrene was used, reaction involves an interesting 1,5‐hydrogen atom transfer (HAT). Mechanistic deuterium‐labeling studies have provided insight into outcome process. addition, cyclobutanes then demonstrated useful selective oxidation processes resulting cyclobutanones γ‐lactones.

Language: Английский

Citations

1