Synthesis of α-Haloboronates by the Halogenation of <i>gem</i>-Diborylalkanes via Tetracoordinate Boron Species

Liao, Shangteng; Liang, Jinchao; Li, Chaokun; Chen, Nan; Yang, Kai; Chen, Jinglong; Song, Qiuling

doi:10.1021/acs.orglett.3c00982

Org. Lett.

2023

DOI: 10.1021/acs.orglett.3c00982

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Synthesis of α-Haloboronates by the Halogenation of gem-Diborylalkanes via Tetracoordinate Boron Species

Shangteng Liao

Jinchao Liang

Chaokun Li

et al.

Abstract: α-Haloboronates have a wide range of applications in organic chemistry as synthetic synthons; however, traditional synthetic methods of α-haloboronates are harsh and complicated. Herein, we used n BuLi as the nucleophilic reagent to attack the boron atom in gem-diborylalkanes to form tetracoordinate boron species and successfully achieved α-chloroboronates and αbromoboronates with readily accessible electrophilic halogen reagents (NCS and NBS). The reaction is transition-metal-free and features a broad substra… Show more

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Cited by 8 publications

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“…Lastly, Song et al. developed the synthesis of α-chloro or bromo boronates from n -butyllithium-activated geminal bis(boronates) …”

mentioning

confidence: 99%

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

Gao,

Li,

et al. 2023

J. Org. Chem.

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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 a visible light-induced C−H bromination reaction of readily available benzyl boronic esters. This method features high yields, mild conditions, simple operation, and good functional group tolerance. The analogous chlorides and iodides can be accessed via Finkelstein reaction. Synthesis of halogenated geminal diborons has also been demonstrated.

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“…Lastly, Song et al. developed the synthesis of α-chloro or bromo boronates from n -butyllithium-activated geminal bis(boronates) …”

mentioning

confidence: 99%

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

Gao,

Li,

et al. 2023

J. Org. Chem.

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Mechanochemical Synthesis of α‐halo Alkylboronic Esters

Zhao,

Yang,

Wang

et al. 2024

Advanced Science

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

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

et al. 2023

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Operationally simple strategies to assemble boron containing organic frameworks are highly enabling in organic 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 to access organoborons via adjacent C−C bond formation. Direct light‐enabled α‐activation is currently contingent on photo‐ or transition metal‐catalysis activation to efficiently generate radical species. Here, we disclose a facile activation of α‐halo boronic esters using only visible light and a simple Lewis base to enable homolytic scission. Intermolecular addition to styrenes facilitates the rapid construction of highly versatile E‐allylic boronic esters. The simplicity of activation permits the strategic merger of this construct with selective energy transfer catalysis to enable the complimentary stereodivergent synthesis of Z‐allylic boronic esters.

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Synthesis of α-Haloboronates by the Halogenation of gem-Diborylalkanes via Tetracoordinate Boron Species

Cited by 8 publications

References 57 publications

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

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

Mechanochemical Synthesis of α‐halo Alkylboronic Esters

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

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