Metal‐Free Stereoconvergent C−H Borylation of Enamides DOI Open Access

Tianhang Wang,

Zhengjun Wang,

Minyan Wang

et al.

Angewandte Chemie, Journal Year: 2023, Volume and Issue: 135(44)

Published: Sept. 18, 2023

Abstract Enamides, functional derivatives of enamines, play a significant role as synthetic targets. However, the stereoselective synthesis these molecules has posed longstanding challenge in organic chemistry, particularly for acyclic enamides that are less thermodynamically stable. In this study, we present general strategy constructing β‐borylenamides by C−H borylation, which provides versatile platform generating stereodefined enamides. Our approach involves utilization metalloid borenium cation, generated through reaction BBr 3 and presence two different additives, avoiding any exogenous catalyst. Importantly, stereoconvergent nature methodology allows use starting materials with mixed E/Z configurations, thus highlighting unique advantage chemistry. Mechanistic investigations have shed light on pivotal roles played reactive boron species, phenomenon stereoconvergence.

Language: Английский

Ir-Catalyzed, Nitrogen-Directed C(sp3)–H and C(sp2)–H Borylation with a Spiro-Fluorene-Indenoindenyl Ligand DOI Creative Commons

Tomonori Inoue,

Yu Sato, Yuki Nagashima

et al.

ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 4061 - 4068

Published: Feb. 21, 2025

Language: Английский

Citations

1
Metal‐Free Stereoconvergent C−H Borylation of Enamides DOI

Tianhang Wang,

Zhengjun Wang,

Minyan Wang

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(44)

Published: Sept. 18, 2023

Enamides, functional derivatives of enamines, play a significant role as synthetic targets. However, the stereoselective synthesis these molecules has posed longstanding challenge in organic chemistry, particularly for acyclic enamides that are less thermodynamically stable. In this study, we present general strategy constructing β-borylenamides by C-H borylation, which provides versatile platform generating stereodefined enamides. Our approach involves utilization metalloid borenium cation, generated through reaction BBr3 and presence two different additives, avoiding any exogenous catalyst. Importantly, stereoconvergent nature methodology allows use starting materials with mixed E/Z configurations, thus highlighting unique advantage chemistry. Mechanistic investigations have shed light on pivotal roles played reactive boron species, phenomenon stereoconvergence.

Language: Английский

Citations

14
Metal-Free ortho C–H Borylation of Thiobenzamides DOI

Jianxing Lv,

Yixuan Liang,

Y. OUYANG

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(18), P. 3709 - 3714

Published: May 1, 2024

A BBr3-mediated S-directed ortho C–H borylation of thiobenzamides was developed. variety ortho-borylated were obtained in moderate to good yields with a wide functional group tolerance under simple and metal-free conditions. This transformation provided convenient practical route important functionalized thiobenzamides.

Language: Английский

Citations

4
BX3-mediated borylation for the synthesis of organoboron compounds DOI
Chunhua Yang

Organic Chemistry Frontiers, Journal Year: 2023, Volume and Issue: 10(23), P. 6010 - 6020

Published: Jan. 1, 2023

This review summarizes the recent progress in borylation driven by BX 3 fields of organic synthesis and drug synthesis.

Language: Английский

Citations

10
BBr3-Mediated ortho C–H Borylation of Benzamides DOI
Yixuan Liang,

Chengyu Du,

C. Dong

et al.

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

Published: April 25, 2025

We have developed a BBr3-mediated, metal-free ortho C-H borylation of benzamides, enabling the synthesis wide range ortho-borylated benzamides in moderate to good yields. This transformation offers convenient strategy for accessing functionalized which are valuable intermediates pharmaceuticals, agrochemicals, and fine chemical synthesis.

Language: Английский

Citations

0
Regioselective ortho halogenation of N-aryl amides and ureas via oxidative halodeboronation: harnessing boron reactivity for efficient C–halogen bond installation DOI Creative Commons

Ganesh Shinde,

Ganesh S. Ghotekar, Francoise M. Amombo Noa

et al.

Chemical Science, Journal Year: 2023, Volume and Issue: 14(46), P. 13429 - 13436

Published: Jan. 1, 2023

The installation of the C-halogen bond at ortho position N-aryl amides and ureas represents a tool to prepare motifs that are ubiquitous in biologically active compounds. To construct such prevalent bonds, most methods require use precious metals multistep process. Here we report novel protocol for long-standing challenge regioselective halogenation using an oxidative halodeboronation. By harnessing reactivity boron over nitrogen, merge carbonyl-directed borylation with consecutive halodeboronation, enabling precise introduction C-X desired ureas. This method offers efficient, practical, scalable solution synthesizing halogenated N-heteroarenes under mild conditions, highlighting superiority directing regioselectivity reaction.

Language: Английский

Citations

8
Ortho Arylation of N‐Aryl Amides and the Construction of Diagonal Tetraarylbenzenediamines and N‐Doped Fulminenes via BBr3‐Derived Dibromoboracycles DOI Creative Commons

Ganesh Shinde,

Ganesh S. Ghotekar, Henrik Sundén

et al.

Chemistry - A European Journal, Journal Year: 2024, Volume and Issue: 31(8)

Published: Nov. 8, 2024

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 aryl amides. However, suffer from issues such as lack selectivity, reliance on stoichiometric oxidants, requirement for excess reagents harsh reaction conditions. overcome challenges, we present a novel highly selective protocol N-aryl amides ureas. high selectivity originates directed installation BBr3 to form boracycle, then undergoes cross-coupling with an halide. Our method offers significant advantages, including mild conditions, excellent site-specificity, scalability. demonstrates broad compatibility diverse range readily accessible functionalized anilides iodides, evidenced by 55 successful examples yielding products 30-95 % range. Furthermore, our methodology surpasses conventional approaches facilitating one-pot diagonal diarylation dianilides. This capability unlocks construction previously unattainable systems, serve valuable precursors tetraarylbenzenediamines N-doped fulminenes, two crucial compound classes materials science.

Language: Английский

Citations

1
Transforming cyclopropanes to enamides via σ-C–C bond eliminative borylation DOI Creative Commons

Shuyu Kang,

Jiahang Lv,

Tianhang Wang

et al.

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: Aug. 27, 2024

Recent strides in C–H borylation have significantly expanded our toolkit for the preparation of organoboronates. Nevertheless, avenues alternative to obtain these compounds via σ-C–C cleavage, thereby facilitating molecular scaffold editing, remain scarce. Several methodologies been proposed hydroboration cyclopropanes by activating C–C bonds, conventionally relying on noble and hazardous metal catalysts control reaction outcomes. Here, we present a strategy crafting stereochemically precise γ-borylenamides through ring-opening avoiding any metallic entities. Boryl species, generated ternary with BCl3, cyclopropanes, tertiary amine, selectively undergo bond eliminative under directing N-acyl group, ensuring enhanced selectivity efficiency along pathway. Such inherently stereoconvergent approach accommodates precursors diverse geometries, including cis/trans isomeric blends. authors report without

Language: Английский

Citations

0
Metal‐Free Stereoconvergent C−H Borylation of Enamides DOI Open Access

Tianhang Wang,

Zhengjun Wang,

Minyan Wang

et al.

Angewandte Chemie, Journal Year: 2023, Volume and Issue: 135(44)

Published: Sept. 18, 2023

Abstract Enamides, functional derivatives of enamines, play a significant role as synthetic targets. However, the stereoselective synthesis these molecules has posed longstanding challenge in organic chemistry, particularly for acyclic enamides that are less thermodynamically stable. In this study, we present general strategy constructing β‐borylenamides by C−H borylation, which provides versatile platform generating stereodefined enamides. Our approach involves utilization metalloid borenium cation, generated through reaction BBr 3 and presence two different additives, avoiding any exogenous catalyst. Importantly, stereoconvergent nature methodology allows use starting materials with mixed E/Z configurations, thus highlighting unique advantage chemistry. Mechanistic investigations have shed light on pivotal roles played reactive boron species, phenomenon stereoconvergence.

Language: Английский

Citations

0