477841-90-0

Basic information

• Product Name: 4-Bromobenzylboronic acid pinacol ester
• Synonyms: 4-bromobenzylboronic acid pinacol ester;2-(4-Bromobenzyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane;2-[(4-broMophenyl)Methyl]-4,4,5,5-tetraMethyl-1,3,2-dioxaborolane
• CAS NO: 477841-90-0
• Molecular Formula: C₁₃H₁₈BBrO₂
• Molecular Weight: 297
• Mol File: 477841-90-0.mol

Chemical Properties

• Boiling Point: 321 °C
• Flash Point: 148 °C
• Appearance: /
• Density: 1.26
• Storage Temp.: 2-8°C
• CAS DataBase Reference: 4-Bromobenzylboronic acid pinacol ester(CAS DataBase Reference)
• NIST Chemistry Reference: 4-Bromobenzylboronic acid pinacol ester(477841-90-0)
• EPA Substance Registry System: 4-Bromobenzylboronic acid pinacol ester(477841-90-0)

Safety Data

• Hazardous Substances Data: 477841-90-0(Hazardous Substances Data)

Usage

Uses

Used in Organic Synthesis:
4-Bromobenzylboronic acid pinacol ester is used as a reagent for Suzuki-Miyaura cross-coupling reactions, facilitating the synthesis of various biaryl compounds. Its capacity to form stable complexes with diols makes it a valuable component in creating complex organic structures.
Used in Pharmaceutical and Agrochemical Synthesis:
In the pharmaceutical and agrochemical industries, 4-Bromobenzylboronic acid pinacol ester is utilized as a building block for the synthesis of new compounds. Its versatility in forming C-C bonds is crucial for the development of innovative drugs and agrochemicals.
Used in Anticancer Research:
4-Bromobenzylboronic acid pinacol ester is investigated for its potential anticancer properties, serving as a lead compound in the development of new anticancer agents. Its exploration in this field underscores the compound's potential to contribute to cancer treatment and research.

Upstream product

• 589-15-1 1-bromomethyl-4-bromobenzene 
• 25015-63-8 4,4,5,5-tetramethyl-[1,3,2]-dioxaboralane 
• 73183-34-3 bis(pinacol)diborane 
• 76-09-5 2,3-dimethyl-2,3-butane diol 
• 106-38-7 para-bromotoluene 
• 5467-74-3 4-Bromophenylboronic acid 
• 18107-18-1 diazomethyl-trimethyl-silane 
• 19350-68-6 p-bromobenzaldehyde tosylhydrazone 
• 1122-91-4 4-bromo-benzaldehyde 

Downstream Products

• 873-75-6 4-bromobenzenemethanol 
• 1878-68-8 2-(4-bromophenyl)-acetic acid 

Relevant articles and documents

Arene borylation through C–H activation using Cu3(BTC)2 as heterogeneous catalyst

C–H borylation by diborane is an important process to access organoboron compounds. Noble metals, including Ir and Rh-based complexes either in the form of homogeneous or heterogeneous catalysts, have been reported to promote arene C–H borylation. Recently, metal organic frameworks (MOFs) having Ir and Co as active sites have been used as catalysts, but they require co-catalysts. In the present study, commercially available Cu3(BTC)2 (BTC: 1,3,5-benzenetricarboxylate) MOF is reported as an effective catalyst to promote borylation of arenes through C–H activation employing bis(pinacolato)diboron (1) as reagent leading to benzylic and aromatic borylation products. Interestingly, other related MOFs like MIL-101(Cr) and Al(OH)(BDC) (BDC: 1,4-benzenedicarboxylate) do not exhibit catalytic activity under identical conditions. Mechanistic studies using in-situ IR spectroscopy reveal that Cu ions play a crucial role in activating the arene and B–B bond in 1.

Photochemical Radical C–H Halogenation of Benzyl N-Methyliminodiacetyl (MIDA) Boronates: Synthesis of α-Functionalized Alkyl Boronates

α-Haloboronates are useful organic synthons that can be converted to a diverse array of α-substituted alkyl borons. Methods to α-haloboronates are limiting and often suffer from harsh reaction conditions. Reported herein is a photochemical radical C-H halogenation of benzyl N-methyliminodiacetyl (MIDA) boronates. Fluorination, chlorination, and bromination reactions were effective by using this protocol. Upon reaction with different nucleophiles, the C?Br bond in the brominated product could be readily transformed to a series of C?C, C?O, C?N, C?S, C?P, and C?I bonds, some of which are difficult to forge with α-halo sp2-B boronate esters. An activation effect of B(MIDA) moiety was found.

Decarboxylative Borylation of Stabilized and Activated Carbon Radicals

Redox-active esters (RAEs) as active radical precursors have been extensively studied for C?B bond formations. However, the analogous transformations of stabilized radicals from the corresponding acid precursors remain challenging owing to the strong preference towards single-electron oxidation to the stable carbocations. This work describes a general strategy for rapid access to various aliphatic and aromatic boronic esters by mild photoinduced decarboxylative borylation. Both aryl and alkyl radicals could be generated from the leaving group-assisted N-hydroxybenzimidoyl chloride esters, even α-CF3 substituted substrates could be activated for further elaboration.

Metal-Free Direct Deoxygenative Borylation of Aldehydes and Ketones

Direct conversion of aldehydes and ketones into alkylboronic esters via deoxygenative borylation represents an unknown yet highly desirable transformation. Herein, we present a one-step and metal-free method for carbonyl deoxy-borylation under mild conditions. A wide range of aromatic aldehydes and ketones are tolerated and successfully converted into the corresponding benzylboronates. By the same deoxygenation manifold with aliphatic aldehydes and ketones, we also enable a concise synthesis of 1,1,2-tris(boronates), a family of compounds that currently lack efficient synthetic methods. Given its simplicity and versatility, we expect that this novel borylation approach could show great promise in organoboron synthesis and inspire more carbonyl deoxygenative transformations in both academic and industrial settings.

CU-AND NI-CATALYZED DECARBOXYLATIVE BORYLATION REACTIONS

The invention is directed to methods of converting a carboxylic acid group in a compound, via a redox active ester, to a corresponding boronic ester by treatment with bis(pinacolato)diboron-alkyllithium complex in the presence of a ligand, a Ni(ll) salt or a copper salt, and an Mg(ll) salt, in the presence of an alkyllithium or a lithium hydroxide or alkoxide salt. The product pinacolato boronate ester can be cleaved to provide a boronic acid. The invention is also directed to methods of preparing various compounds of medical value comprising boronic acid groups, and to novel boronic-acid containing compounds of medicinal value, including an atorvastatin boronic acid analog, a vancomycin aglycone boronic acid analog, and boronic acid containing elastase inhibitors mCBK319, mCBK320, mCBK323, and RPX-7009.

IMIDAZOPYRAZINONES, PYRAZOLOPYRIMIDINONES AND PYRAZOLOPYRIDINONES AS PDE1 INHIBITORS

The present invention provides compounds according to formula (I) below that are PDE1 enzyme inhibitors and their use as medicaments, in particular for the treatment of neurodegenerative disorders and psychiatric disorders. The present invention also provides pharmaceutical compositions comprising compounds of the invention and methods of treating disorders using the compounds of the invention.

Visible-Light-Mediated Aerobic Oxidation of Organoboron Compounds Using in Situ Generated Hydrogen Peroxide

A simple and general visible-light-mediated oxidation of organoboron compounds has been developed with rose bengal as the photocatalyst, substoichiometric Et3N as the electron donor, as well as air as the oxidant. This mild and metal-free protocol shows a broad substrate scope and provides a wide range of aliphatic alcohols and phenols in moderate to excellent yields. Notably, the robustness of this method is demonstrated on the stereospecific aerobic oxidation of organoboron compounds.

Copper(II)-Catalyzed Asymmetric Photoredox Reactions: Enantioselective Alkylation of Imines Driven by Visible Light

Asymmetric photoredox catalysis offers exciting opportunities to develop new synthetic approaches to chiral molecules through novel reaction pathways. Employing the first-row transition metal complexes as the chiral photoredox catalysts remains, however, a formidable challenge, although these complexes are economic, environmentally friendly, and often exhibit special reactivities. We report in this Article the development of one class of highly efficient asymmetric/photoredox bifunctional catalysts based on the copper(II) bisoxazoline complexes (CuII-BOX) for the light-induced enantioselective alkylation of imines. The reactions proceed under very mild conditions and without a need for any other photosensitizer. The simple catalytic system and readily tunable chiral ligands enable a significantly high level of enantioselectivity for the formation of chiral amine products bearing a tetrasubstituted carbon stereocenter (36 examples, up to 98% ee). Overall, the CuII-BOX catalysts initiate the radical generation, and also govern the subsequent stereoselective transformations. This strategy utilizing chiral complexes comprised of a first-row transition metal and a flexible chiral ligand as the asymmetric photoredox catalysts provides an effective platform for the development of green asymmetric synthetic methods.

Decarboxylative borylation

The widespread use of alkyl boronic acids and esters is frequently hampered by the challenges associated with their preparation.We describe a simple and practical method to rapidly access densely functionalized alkyl boronate esters from abundant carboxylic substituents. This broad-scope nickel-catalyzed reaction uses the same activating principle as amide bond formation to replace a carboxylic acid moiety with a boronate ester. Application to peptides allowed expedient preparations of a-amino boronic acids, often with high stereoselectivity, thereby facilitating synthesis of the alkyl boronic acid drugs Velcade and Ninlaro as well as a boronic acid version of the iconic antibiotic vancomycin. The reaction also enabled the discovery and extensive biological characterization of potent human neutrophil elastase inhibitors, which offer reversible covalent binding properties.