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
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
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
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
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
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
Elsevier eBooks, Год журнала: 2025, Номер unknown
Опубликована: Янв. 1, 2025
Язык: Английский
Процитировано
0
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
Molecular Catalysis, Год журнала: 2024, Номер 557, С. 113954 - 113954
Опубликована: Фев. 24, 2024
Язык: Английский
Процитировано
1
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