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

Ruizeng Zhang,

Hao Zhang,

Pan Xu

и другие.

Organic Letters, Год журнала: 2024, Номер unknown

Опубликована: Дек. 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

Язык: Английский

Dinuclear gold-catalyzed divergent dechlorinative radical borylation of gem-dichloroalkanes DOI Creative Commons
Cheng‐Long Ji, Hongliang Chen, Qi Gao

и другие.

Nature Communications, Год журнала: 2024, Номер 15(1)

Опубликована: Май 2, 2024

The enormous and widespread use of organoboronic acids has prompted the development innovative synthetic methodologies to meet demands on structural diversity functional group tolerance. existing photoinduced defunctionalization radical borylation, typically focused conversion one C-X bond (X= Br, I, or other leaving group) into only C-B bond. Herein, we disclose a divergent dechloroborylation reaction enabled by dinuclear gold catalysis with visible light irradiation. A wide range structurally diverse alkyl boronic, α-chloroboronic, gem-diboronic esters can be synthesized in moderate good yields (up 92%). Its robustness is further demonstrated preparative scale applied late-stage diversification complex molecules. process hinges C-Cl relay activation readily available gem-dichloroalkanes through inner-sphere electron transfer, overcoming redox potential limits unreactive chlorides.

Язык: Английский

Процитировано

15

Direct Light‐Enabled Access to α‐Boryl Radicals: Application in the Stereodivergent Synthesis of Allyl Boronic Esters** DOI Creative Commons

Alessandro Marotta,

Fang Hao,

Callum E. Adams

и другие.

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(34)

Опубликована: Июнь 16, 2023

Abstract Operationally simple strategies to assemble boron containing organic frameworks are highly enabling in synthesis. While conventional retrosynthetic logic has engendered many platforms focusing on the direct formation of C−B bonds, α‐boryl radicals have recently reemerged as versatile open‐shell alternatives access organoborons via adjacent C−C bond formation. Direct light‐enabled α‐activation is currently contingent photo‐ or transition metal‐catalysis activation efficiently generate radical species. Here, we disclose a facile α‐halo boronic esters using only visible light and Lewis base enable homolytic scission. Intermolecular addition styrenes facilitates rapid construction E ‐allylic esters. The simplicity permits strategic merger this construct with selective energy transfer catalysis complimentary stereodivergent synthesis Z

Язык: Английский

Процитировано

22

Simultaneous Stereoinvertive and Stereoselective C(sp3)–C(sp3) Cross-Coupling of Boronic Esters and Allylic Carbonates DOI Creative Commons

Hong‐Cheng Shen,

Ze‐Shu Wang, Adam Noble

и другие.

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(20), С. 13719 - 13726

Опубликована: Май 9, 2024

With increasing interest in constructing more three-dimensional entities, there has been growing cross-coupling reactions that forge C(sp3)–C(sp3) bonds, which leads to additional challenges as it is not just a difficult bond construct but issues of stereocontrol also arise. Herein, we report the stereocontrolled enantioenriched boronic esters with racemic allylic carbonates enabled by iridium catalysis, leading formation bonds single or vicinal stereogenic centers. The method shows broad substrate scope, enabling primary, secondary, and even tertiary be employed, can used prepare any four possible stereoisomers coupled product chiral new method, combines simultaneous enantiospecific reaction nucleophile enantioselective electrophile process, offers solution for stereodivergent two C(sp3) fragments.

Язык: Английский

Процитировано

6

Mechanochemical Synthesis of α‐halo Alkylboronic Esters DOI Creative Commons

Yunyi Zhao,

Zekun Yang, Xin Wang

и другие.

Advanced Science, Год журнала: 2024, Номер 11(33)

Опубликована: Июль 3, 2024

α-halo alkylboronic esters, acting as ambiphilic synthons, play a pivotal role versatile intermediates in fields like pharmaceutical science and organic chemistry. The sequential transformation of carbon-boron carbon-halogen bonds into broad range carbon-X allows for programmable bond formation, facilitating the incorporation multiple substituents at single position streamlining synthesis complex molecules. Nevertheless, synthetic potential these compounds is constrained by limited reaction patterns. Additionally, conventional methods often necessitate use bulk toxic solvents, exhibit sensitivity to air/moisture, rely on expensive metal catalysts, involve extended times. In this report, ball milling technique introduced that overcomes limitations, enabling external catalyst-free multicomponent coupling aryl diazonium salts, alkenes, simple halides. This approach offers general straightforward method obtaining diverse array thereby paving way extensive utilization synthons fine chemicals.

Язык: Английский

Процитировано

6

Construction of α-Halogenated Boronic Esters via Visible Light-Induced C–H Bromination DOI

Feng‐Chen Gao,

Ming Li,

Heng-Yu Gu

и другие.

The Journal of Organic Chemistry, Год журнала: 2023, Номер 88(19), С. 14246 - 14254

Опубликована: Сен. 21, 2023

α-Halogenated boronic esters are versatile building blocks that can be diversified into a wide variety of polyfunctionalized molecules. However, their synthetic potential has been hampered by limited preparation methods. Herein, we report visible light-induced C-H bromination reaction readily available benzyl esters. This method features high yields, mild conditions, simple operation, and good functional group tolerance. The analogous chlorides iodides accessed via Finkelstein reaction. Synthesis halogenated geminal diborons also demonstrated.

Язык: Английский

Процитировано

11

Oxidation of Carbon–Boron Bonds DOI
Du Chen, Chao Liu

Elsevier eBooks, Год журнала: 2025, Номер unknown

Опубликована: Янв. 1, 2025

Язык: Английский

Процитировано

0

Direct Light‐Enabled Access to α‐Boryl Radicals: Application in the Stereodivergent Synthesis of Allyl Boronic Esters** DOI Creative Commons

Alessandro Marotta,

Fang Hao,

Callum E. Adams

и другие.

Angewandte Chemie, Год журнала: 2023, Номер 135(34)

Опубликована: Июнь 16, 2023

Abstract Operationally simple strategies to assemble boron containing organic frameworks are highly enabling in synthesis. While conventional retrosynthetic logic has engendered many platforms focusing on the direct formation of C−B bonds, α‐boryl radicals have recently reemerged as versatile open‐shell alternatives access organoborons via adjacent C−C bond formation. Direct light‐enabled α‐activation is currently contingent photo‐ or transition metal‐catalysis activation efficiently generate radical species. Here, we disclose a facile α‐halo boronic esters using only visible light and Lewis base enable homolytic scission. Intermolecular addition styrenes facilitates rapid construction E ‐allylic esters. The simplicity permits strategic merger this construct with selective energy transfer catalysis complimentary stereodivergent synthesis Z

Язык: Английский

Процитировано

4

Fe(0)-catalyzed radical halosulfonation: Regioselective synthesis of α-halo alkylboronic esters DOI

Jiamin Ma,

Tingting Xia,

Jiaoxiong Li

и другие.

Molecular Catalysis, Год журнала: 2024, Номер 557, С. 113954 - 113954

Опубликована: Фев. 24, 2024

Язык: Английский

Процитировано

1

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

Ruizeng Zhang,

Hao Zhang,

Pan Xu

и другие.

Organic Letters, Год журнала: 2024, Номер unknown

Опубликована: Дек. 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

Язык: Английский

Процитировано

1