Metal-Free <i>ortho</i> C–H Borylation of Thiobenzamides

Lv, Jianxing; Liang, Yixuan; Ouyang, Yepeng; Zhang, Hua

doi:10.1021/acs.orglett.4c00691

Org. Lett.

2024

DOI: 10.1021/acs.orglett.4c00691

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Metal-Free ortho C–H Borylation of Thiobenzamides

Jianxing Lv,

Yixuan Liang,

Yepeng Ouyang

et al.

Abstract: A BBr 3 -mediated S-directed ortho C−H borylation of thiobenzamides was developed. A variety of ortho-borylated thiobenzamides were obtained in moderate to good yields with a wide functional group tolerance under simple and metal-free conditions. This transformation provided a convenient and practical route to important functionalized thiobenzamides.

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Cited by 3 publications

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Ortho Arylation of N‐Aryl Amides and the Construction of Diagonal Tetraarylbenzenediamines and N‐Doped Fulminenes via BBr₃‐Derived Dibromoboracycles

Shinde,

Ghotekar,

Sundén

2024

Chemistry A European J

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The synthesis of biaryl amides, which are prevalent motifs in bioactive molecules, often necessitates lengthy and inefficient procedures. To address these limitations, catalytic C‐H activation protocols have emerged, enabling the direct ortho‐arylation of aryl amides. However, these protocols often suffer from issues such as lack of selectivity, reliance on stoichiometric oxidants, and the requirement for excess reagents and harsh reaction conditions. To overcome these challenges, we present a novel and highly selective protocol for the ortho‐arylation of N‐aryl amides and ureas. The high selectivity originates from the directed installation of BBr3 to form a boracycle, which then undergoes cross‐coupling with an aryl halide. Our method offers significant advantages, including mild reaction conditions, excellent site‐specificity, and scalability. The protocol demonstrates broad compatibility with a diverse range of readily accessible functionalized anilides and aryl iodides, as evidenced by 55 successful examples yielding products in the 30–95% range. Furthermore, our methodology surpasses conventional approaches by facilitating the one‐pot selective diagonal diarylation of dianilides. This capability unlocks the construction of previously unattainable diagonal aryl systems, which serve as valuable precursors for the synthesis of diagonal tetraarylbenzenediamines and N‐doped fulminene, two crucial compound classes in materials science.

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Ortho Arylation of N‐Aryl Amides and the Construction of Diagonal Tetraarylbenzenediamines and N‐Doped Fulminenes via BBr₃‐Derived Dibromoboracycles

Shinde,

Ghotekar,

Sundén

2024

Chemistry A European J

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Boron-Mediated Selective C–H Hydroxylation of 1-Phenyl-1H-Pyrazoles

Wu,

Liu,

Chen

et al. 2024

J. Org. Chem.

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A novel strategy for boron-mediated C−H hydroxylation of 1-phenyl-1H-pyrazoles is presented. The protocol exhibits high efficiency and site exclusivity, offering the corresponding phenols in moderate to excellent yields with wide functional group tolerance under simple and metal-free conditions. Moreover, the hydroxylated products show good derivatization applications. This route provides a convenient and practical way to obtain functionalized 1-phenyl-1H-pyrazoles.

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Metal-free Borylation of α-Naphthamides and Phenylacetic Acid Drug

Maji,

Rawal,

Ghosh

et al. 2024

JACS Au

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Site-selective C–H borylation is an important strategy for constructing molecular diversity in arenes and heteroarenes. Although transition-metal-catalyzed borylation is well explored, developing metal-free strategies remains scarce. Herein, we developed a straightforward approach for BBr 3 -mediated selective C–H borylation of naphthamide and phenyl acetamide derivatives under metal-free conditions. This methodology appears to be economical and cost-effective. Successful borylation of drug molecules such as ibuprofen and indoprofen demonstrates the versatility and utility of this metal-free borylation. An exclusive monoselectivity was observed without a trace of diboration. Despite the possibility of forming a 5-membered boronated intermediate at the ortho -position, the selectively 6-membered intermediate paved the way for the formation of the peri-product, which was further supported by detailed computational investigation.

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Metal-Free ortho C–H Borylation of Thiobenzamides

Cited by 3 publications

References 78 publications

Ortho Arylation of N‐Aryl Amides and the Construction of Diagonal Tetraarylbenzenediamines and N‐Doped Fulminenes via BBr₃‐Derived Dibromoboracycles

Ortho Arylation of N‐Aryl Amides and the Construction of Diagonal Tetraarylbenzenediamines and N‐Doped Fulminenes via BBr₃‐Derived Dibromoboracycles

Boron-Mediated Selective C–H Hydroxylation of 1-Phenyl-1H-Pyrazoles

Metal-free Borylation of α-Naphthamides and Phenylacetic Acid Drug

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Metal-Free ortho C–H Borylation of Thiobenzamides

Cited by 3 publications

References 78 publications

Ortho Arylation of N‐Aryl Amides and the Construction of Diagonal Tetraarylbenzenediamines and N‐Doped Fulminenes via BBr3‐Derived Dibromoboracycles

Ortho Arylation of N‐Aryl Amides and the Construction of Diagonal Tetraarylbenzenediamines and N‐Doped Fulminenes via BBr3‐Derived Dibromoboracycles

Boron-Mediated Selective C–H Hydroxylation of 1-Phenyl-1H-Pyrazoles

Metal-free Borylation of α-Naphthamides and Phenylacetic Acid Drug

Contact Info

Product

Resources

About

Ortho Arylation of N‐Aryl Amides and the Construction of Diagonal Tetraarylbenzenediamines and N‐Doped Fulminenes via BBr₃‐Derived Dibromoboracycles

Ortho Arylation of N‐Aryl Amides and the Construction of Diagonal Tetraarylbenzenediamines and N‐Doped Fulminenes via BBr₃‐Derived Dibromoboracycles