Haloboration ofo‐Alkynyl Phenols Generates Halogenated Bicyclic‐Boronates** DOI Creative Commons
Kang Yuan, Michael J. Ingleson

Angewandte Chemie, Journal Year: 2023, Volume and Issue: 135(17)

Published: March 1, 2023

Abstract Benzoxaborinines are intermediates en‐route to bicyclic boronates that important active pharmaceutical ingredients (APIs). Herein, the haloboration of o ‐alkynyl‐phenols using BX 3 (X=Cl or Br) is disclosed as a route form C4‐X‐benzoxaborinines with good functional group tolerance. Computational studies indicated there two similar in barrier mechanisms: (i) double alkyne followed by retro ‐haloboration; (ii) concerted trans ‐haloboration involving an exogenous chloride source. The C4‐halide these benzoxaborinines useful, one‐pot haloboration‐Negishi cross coupling protocol effective alkyl aryl at C4. Therefore this method useful addition toolbox for synthesising bicyclic‐boronates attracting increasing attention APIs.

Language: Английский

Amides as modifiable directing groups in electrophilic borylation DOI Creative Commons

Saqib A. Iqbal,

Marina Uzelac,

Ismat Nawaz

et al.

Chemical Science, Journal Year: 2023, Volume and Issue: 14(14), P. 3865 - 3872

Published: Jan. 1, 2023

Amide directed C-H borylation using ≥two equiv. of BBr3 forms borenium cations containing a R2N(R')C[double bond, length as m-dash]O→B(Ar)Br unit which has significant Lewis acidity at the carbonyl carbon. This enables reduction amide to an amine hydrosilanes. approach can be applied sequentially in one-pot electrophilic borylation-reduction process, for phenyl-acetylamides generates ortho borylated compounds that directly oxidised 2-(2-aminoethyl)-phenol. Other substrates amenable sequence include mono and diamino-arenes carbazoles. represents simple method make molecules would convoluted access otherwise (e.g. N-octyl-1-BPin-carbazole). Substituent variation is tolerated boron well unit, with diarylborenium also reduction. double borylation-reduction-hydrolysis B,N-polycyclic aromatic hydrocarbons (PAHs), including example where both nitrogen centres contain functionalisable handles (N-H B-OH). therefore useful addition metal-free toolbox accessing intermediates (ArylBPin) novel B,N-PAHs.

Language: Английский

Citations

16
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
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
Directing group controlled regioselective C–H borylation of 2-arylphenolic compounds at room temperature DOI

Jiao Kang,

Jing Liu, Zhilong Chen

et al.

Organic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(15), P. 4249 - 4257

Published: Jan. 1, 2024

The Fe(OTf) 3 -promoted directing group-controlled regioselective C–H borylation of 2-arylarenolic compounds was achieved at room temperature, affording two useful arylboronic acids efficiently.

Language: Английский

Citations

3
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
Haloboration of o‐Alkynyl Phenols Generates Halogenated Bicyclic‐Boronates** DOI Creative Commons
Kang Yuan, Michael J. Ingleson

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(17)

Published: March 1, 2023

Abstract Benzoxaborinines are intermediates en‐route to bicyclic boronates that important active pharmaceutical ingredients (APIs). Herein, the haloboration of o ‐alkynyl‐phenols using BX 3 (X=Cl or Br) is disclosed as a route form C4‐X‐benzoxaborinines with good functional group tolerance. Computational studies indicated there two similar in barrier mechanisms: (i) double alkyne followed by retro ‐haloboration; (ii) concerted trans ‐haloboration involving an exogenous chloride source. The C4‐halide these benzoxaborinines useful, one‐pot haloboration‐Negishi cross coupling protocol effective alkyl aryl at C4. Therefore this method useful addition toolbox for synthesising bicyclic‐boronates attracting increasing attention APIs.

Language: Английский

Citations

7
The Versatile and Strategic O-Carbamate Directed Metalation Group in the Synthesis of Aromatic Molecules: An Update DOI Creative Commons
Ross D. Jansen‐van Vuuren,

Susana Liu,

M. A. Jalil Miah

et al.

Chemical Reviews, Journal Year: 2024, Volume and Issue: 124(12), P. 7731 - 7828

Published: June 12, 2024

The aryl

Language: Английский

Citations

2
Two Directing Groups Used for Metal Catalysed Meta‐C−H Functionalisation Only Effect Ortho Electrophilic C−H Borylation DOI Creative Commons

Saqib A. Iqbal,

Clément R. P. Millet,

Jürgen Pahl

et al.

European Journal of Organic Chemistry, Journal Year: 2022, Volume and Issue: 2022(44)

Published: Oct. 21, 2022

Two templates used in meta-directed C-H functionalisation under metal catalysis do not direct meta-C-H borylation electrophilic conditions. Using BCl3 only Lewis adduct formation with basic sites the template is observed. While combining BBr3 and containing an amide linker led to directed ortho borylation, no pyridyl meta borylation. The selective for of aniline derived unit template, phenylacetyl ring - which would also form a six membered boracycle In absence other aromatics on rings can be achieved. meta-borylation using two indicates higher barrier relative suggests that bespoke enabling may required.

Language: Английский

Citations

10
Borylation–Reduction–Borylation for the Formation of 1,4-Azaborines DOI Creative Commons
Shantaram Kothavale,

Saqib A. Iqbal,

Emily L. Hanover

et al.

Organic Letters, Journal Year: 2023, Volume and Issue: 25(49), P. 8912 - 8916

Published: Dec. 6, 2023

Given the current interest in materials containing 1,4-azaborine units, development of new routes to these structures is important. Carbonyl directed electrophilic borylation using BBr3 a facile method for ortho-borylation N,N-diaryl-amide derivatives. Subsequent addition Et3SiH results carbonyl reduction and then formation 1,4-azaborines that can be protected situ Grignard reagent. Overall, borylation–reduction–borylation one-pot methodology access from simple precursors.

Language: Английский

Citations

5
Haloboration ofo‐Alkynyl Phenols Generates Halogenated Bicyclic‐Boronates** DOI Creative Commons
Kang Yuan, Michael J. Ingleson

Angewandte Chemie, Journal Year: 2023, Volume and Issue: 135(17)

Published: March 1, 2023

Abstract Benzoxaborinines are intermediates en‐route to bicyclic boronates that important active pharmaceutical ingredients (APIs). Herein, the haloboration of o ‐alkynyl‐phenols using BX 3 (X=Cl or Br) is disclosed as a route form C4‐X‐benzoxaborinines with good functional group tolerance. Computational studies indicated there two similar in barrier mechanisms: (i) double alkyne followed by retro ‐haloboration; (ii) concerted trans ‐haloboration involving an exogenous chloride source. The C4‐halide these benzoxaborinines useful, one‐pot haloboration‐Negishi cross coupling protocol effective alkyl aryl at C4. Therefore this method useful addition toolbox for synthesising bicyclic‐boronates attracting increasing attention APIs.

Language: Английский

Citations

0