269409-97-4

Usage

Uses

Used in Pharmaceutical Industry:
2-(4,4,5,5-TETRAMETHYL-1,3,2-DIOXABOROLAN-2-YL)PHENOL is used as a reactant for the synthesis of indolo-fused heterocyclic inhibitors of the polymerase enzyme of hepatitis C. These inhibitors play a crucial role in the development of antiviral drugs to combat hepatitis C virus.
Used in Chemical Research:
In the field of chemical research, 2-(4,4,5,5-TETRAMETHYL-1,3,2-DIOXABOROLAN-2-YL)PHENOL is used as a reactant for studying pi-interactions, electronic structure, and transient UV absorption of subphthalocyanine-borate-bridged ferrocene-fullerene conjugates. These studies contribute to the understanding of molecular interactions and the development of new materials with potential applications in various industries.
Used in Organic Synthesis:
2-(4,4,5,5-TETRAMETHYL-1,3,2-DIOXABOROLAN-2-YL)PHENOL is used as a reactant in the synthesis of subphthalocyanine and fused-ring nicotine derivatives. These compounds have potential applications in various fields, including pharmaceuticals, dyes, and materials science.
Used in Suzuki Coupling Chemistry:
2-(4,4,5,5-TETRAMETHYL-1,3,2-DIOXABOROLAN-2-YL)PHENOL can be widely used in Suzuki coupling chemistry, a type of carbon-carbon bond-forming reaction. This reaction is essential in the synthesis of complex organic molecules, including pharmaceuticals, agrochemicals, and advanced materials.
Used in the Synthesis of Hydroxylated Oligoarene Phosphines:
2-(4,4,5,5-TETRAMETHYL-1,3,2-DIOXABOROLAN-2-YL)PHENOL is used as a reactant in the Suzuki-Miyaura coupling-triflation sequence, reduction, and salt formation for the synthesis of hydroxylated oligoarene phosphines. These phosphines are valuable compounds with potential applications in catalysis and materials science.

InChI:InChI=1/C12H17BO3/c1-11(2)12(3,4)16-13(15-11)9-7-5-6-8-10(9)14/h5-8,14H,1-4H3

Upstream product

• 533-58-4 2-Iodophenol 
• 25015-63-8 4,4,5,5-tetramethyl-[1,3,2]-dioxaboralane 
• 95-55-6 2-amino-phenol 
• 73183-34-3 bis(pinacol)diborane 
• 76-09-5 2,3-dimethyl-2,3-butane diol 
• 89466-08-0 2-hydroxyphenyl boronic acid 
• 10294-34-5 boron trichloride 
• 122-79-2 Phenyl acetate 
• 108-95-2 phenol 
• 95770-20-0 4,4,5,5-tetramethyl-2-phenoxy-1,3,2-dioxaborolane 
• 33837-96-6 methyl thiomethyl ether of phenol 
• 95-56-7 2-hydroxybromobenzene 
• 101-02-0 triphenyl phosphite 
• 13360-92-4 phenyl diphenylphosphinite 

Downstream Products

• 101043-55-4 2-(4-methylphenyl)phenol 
• 1235556-53-2 C₅₆H₄₅BN₆O₄ 
• 83164-95-8 1-carbomethoxy-11-oxatricyclo[6.2.1.0^2,7]undeca-2,4,6,9-tetraene 
• 4706-43-8 1-benzyl-1H-benzotriazole 
• 271-44-3 benzimidazole 
• 1253786-03-6 2-(tert-butyl)-2,3-dihydro-3-phenyl-1,2-benzoisoxazole 
• 1437769-74-8 (2-{[(trifluoromethyl)sulfonyl]oxy}phenyl)boronic acid 
• 19061-38-2 (9s,10s)-9,10-diphenyl-9,10-dihydro-9,10-epoxyanthracene 
• 1437769-72-6 2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl trifluoromethanesulfonate 
• 1245824-39-8 2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl methanesulfonate 
• 444-30-4 2-(trifluoromethyl)phenol 
• 1266741-05-2 4-[3,5-bis(2-hydroxyphenyl)-1,2,4-triazol-1-yl]benzoic acid methyl ester 

Relevant academic research and scientific papers

Ir-Catalyzed Ligand-Free Directed C-H Borylation of Arenes and Pharmaceuticals: Detailed Mechanistic Understanding

An efficient method for Ir-catalyzed ligand free ortho borylation of arenes (such as, 2-phenoxypyridines, 2-anilinopyridines, benzylamines, benzylpiperazines, benzylmorpholines, benzylpyrrolidine, benzylpiperidines, benzylazepanes, α-amino acid derivatives, aminophenylethane derivatives, and other important scaffolds) and pharmaceuticals has been developed. The reaction underwent via an interesting mechanistic pathway, as revealed by the detailed mechanistic investigations by using kinetic isotope studies and DFT calculations. The catalytic cycle is found to involve the intermediacy of an Ir-boryl complex where the substrate C-H activation is the turnover determining step, intriguingly without any appreciable primary KIE. The method displays a broad range of substrate scope and functional group tolerance. Numerous late-stage borylation of various important molecules and drugs were achieved using this developed strategy. The borylated compounds were further converted into more valuable functionalities. Moreover, utilizing the benefit of the B-N intramolecular interaction of the mono borylated compounds, an operationally simple method has been developed for the selective diborylation of 2-phenoxypyridines and numerous functionalized arenes. Furthermore, the synthetic utility has been showcased with the removal of the pyridyl directing group from the borylated product to achieve ortho borylated phenol along with the ipso-borylation for the preparation of 1,2-diborylated benzene.

Ligand-Regulated Palladium-Catalyzed Regiodivergent Hydroarylation of the Distal Double Bond of Allenamides with Aryl Boronic Acid

The ligand-regulated regiodivergent hydroarylation of the distal double bond of allenamides with aryl boronic acid was achieved in the presence of palladium(II) catalysts, delivering a variety of functionalized enamide with excellent E selectivity and Markovnikov/anti-Markovnikov selectivity. Two possible coordination intermediates were proposed to be responsible for the regiodivergent hydroarylation: (1) The coordination Intermediate I, which was proposed to be formed through the coordination of MeCN, distal double bond, phenyl to palladium, led to the aryl group away from the Intermediate I, inducing excellent E selectivity and anti-Markovnikov selectivity. (2) A switch of regioselectivity to 1,2-Markovnikov hydroarylation was obtained using bidentate phosphine ligand (dppf or Xantphos). The formed coordination Intermediate II led to the N-tether away from the Intermediate II and at the trans position of aryl, resulting in excellent E selectivity and Markovnikov selectivity. Meanwhile, tentative investigation on the mechanism proved that the hydron source of this hydroarylation is more likely to be boronic acid. The transmetallation between aryl boronic acid and palladium catalyst was the initial step of this transformation.

Cross-Coupling through Ag(I)/Ag(III) Redox Manifold

In ample variety of transformations, the presence of silver as an additive or co-catalyst is believed to be innocuous for the efficiency of the operating metal catalyst. Even though Ag additives are required often as coupling partners, oxidants or halide scavengers, its role as a catalytically competent species is widely neglected in cross-coupling reactions. Most likely, this is due to the erroneously assumed incapacity of Ag to undergo 2e? redox steps. Definite proof is herein provided for the required elementary steps to accomplish the oxidative trifluoromethylation of arenes through AgI/AgIII redox catalysis (i. e. CEL coupling), namely: i) easy AgI/AgIII 2e? oxidation mediated by air; ii) bpy/phen ligation to AgIII; iii) boron-to-AgIII aryl transfer; and iv) ulterior reductive elimination of benzotrifluorides from an [aryl-AgIII-CF3] fragment. More precisely, an ultimate entry and full characterization of organosilver(III) compounds [K]+[AgIII(CF3)4]? (K-1), [(bpy)AgIII(CF3)3] (2) and [(phen)AgIII(CF3)3] (3), is described. The utility of 3 in cross-coupling has been showcased unambiguously, and a large variety of arylboron compounds was trifluoromethylated via [AgIII(aryl)(CF3)3]? intermediates. This work breaks with old stereotypes and misconceptions regarding the inability of Ag to undergo cross-coupling by itself.

Ruthenium-catalyzed regio- And site-selective: Ortho C-H borylation of phenol derivatives

Efficient synthesis of o-borylphenols is achieved through the Ru-catalyzed regio- and site-selective sp2 C-H borylation of aryl diphenylphosphinites followed by removal of the phosphorus directing group. A successful application to aryl phosphites enables practical one-pot borylation of phenols, demonstrating high synthetic utility of this protocol.

Redox-Neutral Borylation of Aryl Sulfonium Salts via C-S Activation Enabled by Light

Reported here is a novel photoinduced strategy for the borylation of aryl sulfonium salts using bis(pinacolato)diboron as the boron source. This method exploits redox-neutral aryl sulfoniums to gain access to aryl radicals via C-S bond activation upon photoexcitation under transition-metal-free conditions. Therefore, it grants access to diverse arylboronate esters with good performance from easily available aryl sulfoniums accompanied by mild conditions, operational simplicity, and easy scalability.

Hydrogenation of (Hetero)aryl Boronate Esters with a Cyclic (Alkyl)(amino)carbene–Rhodium Complex: Direct Access to cis-Substituted Borylated Cycloalkanes and Saturated Heterocycles

We herein report the hydrogenation of substituted aryl- and heteroaryl boronate esters for the selective synthesis of cis-substituted borylated cycloalkanes and saturated heterocycles. A cyclic (alkyl)(amino)carbene-ligated rhodium complex with two dimethyl groups at the ortho-alkyl scaffold of the carbene showed high reactivity in promoting the hydrogenation, thereby enabling the hydrogenation of (hetero)arenes with retention of the synthetically valuable boronate group. This process constitutes a clean, atom-economic, as well as chemo- and stereoselective route for the generation of cis-configured, diversely substituted borylated cycloalkanes and saturated heterocycles that are usually elusive and difficult to prepare.

Bedford-type palladacycle-catalyzed miyaura borylation of aryl halides with tetrahydroxydiboron in water

A mild aqueous protocol for palladium catalyzed Miyaura borylation of aryl iodides, aryl bromides and aryl chlorides with tetrahydroxydiboron (BBA) as a borylating agent is developed. The developed methodology requires low catalyst loading of Bedford-type palladacycle catalyst (0.05 mol %) and works best under mild reaction conditions at 40 °C in short time of 6 h in water. In addition, our studies show that for Miyaura borylation using BBA in aqueous condition, maintaining a neutral reaction pH is very important for reproducibility and higher yields of corresponding borylated products. Moreover, our protocol is applicable for a broad range of aryl halides, corresponding borylated products are obtained in excellent yields up to 93% with 29 examples demonstrating its broad utility and functional group tolerance.

Cobalt-Catalyzed C-F Bond Borylation of Aryl Fluorides

A mild and practical cobalt-catalyzed defluoroborylation of fluoroarenes is presented for the first time. The method permits straightforward functionalization of fluoroarenes, with high selectivity for borylation of C-F over C-H bonds, and a tolerance for aerobic conditions. Furthermore, two-step 18F-fluorination was achieved for expanding the scope of 18F-positron emission tomography probes.

Iridium/Bipyridine-Catalyzed ortho-Selective C-H Borylation of Phenol and Aniline Derivatives

An iridium-catalyzed ortho-selective C-H borylation of phenol and aniline derivatives has been successfully developed. Iridium/bipyridine-catalyzed C-H borylation generally occurred at the meta- and para-positions of aromatic substrates. Introduction of an electron-withdrawing substituent on the bipyridine-type ligand and a methylthiomethyl group on the hydroxy and amino groups of the phenol and aniline substrates, however, dramatically altered the regioselectivity, affording exclusively ortho-borylated products. The reaction proceeded in good to excellent yields with good functional group tolerance. C-H borylation was applied to the synthesis of a calcium receptor modulator.

Ir-Catalyzed ortho-Borylation of Phenols Directed by Substrate-Ligand Electrostatic Interactions: A Combined Experimental/in Silico Strategy for Optimizing Weak Interactions

A strategy for affecting ortho versus meta/para selectivity in Ir-catalyzed C-H borylations (CHBs) of phenols is described. From selectivity observations with ArylOBpin (pin = pinacolate), it is hypothesized that an electrostatic interaction between the partial negatively charged OBpin group and the partial positively charged bipyridine ligand of the catalyst favors ortho selectivity. Experimental and computational studies designed to test this hypothesis support it. From further computational work a second generation, in silico designed catalyst emerged, where replacing Bpin with Beg (eg = ethylene glycolate) was predicted to significantly improve ortho selectivity. Experimentally, reactions employing B2eg2 gave ortho selectivities > 99%. Adding triethylamine significantly improved conversions. This ligand-substrate electrostatic interaction provides a unique control element for selective C-H functionalization.