190788-58-0

Basic information

• Product Name: 4-(METHYLTHIO)PHENYLBORONIC ACID PINACOLATE
• Synonyms: 4-THIOANISOLEBORONIC ACID, PINACOL ESTER;4-(METHYLTHIO)PHENYLBORONIC ACID PINACOLATE;4-Methylthiophenylboronic acid,pinacol ester;4,4,5,5-TetraMethyl-2-(4-(Methylthio)phenyl)-1,3,2-dioxaborolane
• CAS NO: 190788-58-0
• Molecular Formula: C₁₃H₁₉BO₂S
• Molecular Weight: 250.16
• EINECS: 808-573-6
• Product Categories: Boronic Acid
• Mol File: 190788-58-0.mol

Chemical Properties

• Melting Point: 35.1-35.9 °C
• Boiling Point: 344.5°C at 760 mmHg
• Flash Point: 162.2°C
• Appearance: /
• Density: 1.06g/cm³
• Vapor Pressure: 0.00013mmHg at 25°C
• Refractive Index: 1.525
• Storage Temp.: under inert gas (nitrogen or Argon) at 2–8 °C
• CAS DataBase Reference: 4-(METHYLTHIO)PHENYLBORONIC ACID PINACOLATE(CAS DataBase Reference)
• NIST Chemistry Reference: 4-(METHYLTHIO)PHENYLBORONIC ACID PINACOLATE(190788-58-0)
• EPA Substance Registry System: 4-(METHYLTHIO)PHENYLBORONIC ACID PINACOLATE(190788-58-0)

Safety Data

• Hazard Codes: Xn
• Statements: 22
• WGK Germany: 3
• Hazardous Substances Data: 190788-58-0(Hazardous Substances Data)

Usage

Uses

Used in Organic Synthesis:
4-(METHYLTHIO)PHENYLBORONIC ACID PINACOLATE is used as a reagent in the Suzuki-Miyaura cross-coupling reaction, a widely employed method for forming carbon-carbon bonds. This reaction is crucial for the synthesis of complex organic molecules, including pharmaceuticals, agrochemicals, and advanced materials.
Used in Pharmaceutical Industry:
In the pharmaceutical industry, 4-(METHYLTHIO)PHENYLBORONIC ACID PINACOLATE is used as a building block for the development of new drugs. Its ability to form carbon-carbon bonds through the Suzuki-Miyaura cross-coupling reaction enables the creation of diverse molecular structures with potential therapeutic properties.
Used in Antitumor Research:
4-(METHYLTHIO)PHENYLBORONIC ACID PINACOLATE has been studied for its potential antitumor properties. Researchers are exploring its ability to inhibit the growth of cancer cells and its potential use in the development of novel anticancer agents.
Used in Antifungal Applications:
This chemical compound has also been investigated for its antifungal properties. It shows promise in the development of new antifungal agents to combat fungal infections, which are a significant concern in various industries, including agriculture and healthcare.
Handling and Storage:
4-(METHYLTHIO)PHENYLBORONIC ACID PINACOLATE is typically handled and stored under standard laboratory conditions and precautions to ensure its stability and reactivity. Proper handling and storage practices are essential to maintain the compound's integrity and effectiveness in various applications.

InChI:InChI=1/C13H19BO2S/c1-12(2)13(3,4)16-14(15-12)10-6-8-11(17-5)9-7-10/h6-9H,1-5H3

Upstream product

• 17763-67-6 Phenyl triflate 
• 57728-76-4 4-(methylthio)phenyl trifluoromethanesulfonate 
• 76-09-5 2,3-dimethyl-2,3-butane diol 
• 104-95-0 (4-bromophenyl)thioanisole 
• 51901-85-0 bromocatecholborane 
• 7440-66-6 zinc 
• 100-68-5 methyl-phenyl-thioether 
• 73183-34-3 bis(pinacol)diborane 
• 2432-51-1 ethylthioacetic acid methyl ester 
• 68716-49-4 p-bromophenylboronic acid pinacol ester 
• 123-09-1 4-chlorophenyl methyl sulfide 
• 35371-03-0 4-iodothioanisole 
• 13205-48-6 4-(methylthio)benzoic acid 
• 1442-06-4 4-(methylthio)benzoyl chloride 

Downstream Products

• 3795-79-7 methyl 4-(methylthio)benzoate 
• 1016641-70-5 4,4,5,5-tetramethyl-2-(4-(methylsulfinyl)phenyl)-1,3,2-dioxaborolane 
• 171364-82-2 4-cyanophenylboronic acid pinacol ester 
• 58897-52-2 6-(4-(methylthio)phenyl)pyridazin-3(2H)-one 
• 13205-48-6 4-(methylthio)benzoic acid 
• 603143-27-7 (4,4,5,5-tetramethyl-2-[4-(methylsulfonyl)phenyl])-1,3,2-dioxaborolane 
• 1041009-21-5 C₁₂H₁₄OS 
• 99770-93-1 benzene-1,4-diboronic acid bispinacol ester 
• 256387-80-1 8⁴,1⁴-dimethylsulfanyl-7³,6²,5³,4²,3³,2²-hexa(tert-butoxycarbonylmethoxy)-p-octiphenyl 
• 256387-82-3 8⁴,1⁴-dimethylsulfanyl-7³,6²,5³,4²,3³,2²-hexa(18-azacrown-6-N-carbonylmethoxy)-p-octiphenyl 

Relevant articles and documents

Unveiling Extreme Photoreduction Potentials of Donor-Acceptor Cyanoarenes to Access Aryl Radicals from Aryl Chlorides

Since the seminal work of Zhang in 2016, donor-acceptor cyanoarene-based fluorophores, such as 1,2,3,5-tetrakis(carbazol-9-yl)-4,6-dicyanobenzene (4CzIPN), have been widely applied in photoredox catalysis and used as excellent metal-free alternatives to noble metal Ir- and Ru-based photocatalysts. However, all the reported photoredox reactions involving this chromophore family are based on harnessing the energy from a single visible light photon, with a limited range of redox potentials from -1.92 to +1.79 V vs SCE. Here, we document the unprecedented discovery that this family of fluorophores can undergo consecutive photoinduced electron transfer (ConPET) to achieve very high reduction potentials. One of the newly synthesized catalysts, 2,4,5-tri(9H-carbazol-9-yl)-6-(ethyl(phenyl)amino)isophthalonitrile (3CzEPAIPN), possesses a long-lived (12.95 ns) excited radical anion form, 3CzEPAIPN?-*, which can be used to activate reductively recalcitrant aryl chlorides (Ered ≈ -1.9 to -2.9 V vs SCE) under mild conditions. The resultant aryl radicals can be engaged in synthetically valuable aromatic C-B, C-P, and C-C bond formation to furnish arylboronates, arylphosphonium salts, arylphosphonates, and spirocyclic cyclohexadienes.

Iridium-Catalyzed ortho-C-H Borylation of Thioanisole Derivatives Using Bipyridine-Type Ligand

A simple iridium catalytic system was developed that allows for a variety of 2-borylthioanisoles to be easily synthesized via ortho-selective C-H borylation of thioanisole derivatives. Once introduced, boryl and methylthio groups were converted by palladium-catalyzed transformations. Density functional theory calculations revealed that weak interactions, such as hydrogen bonding between the C-H bond of the SCH3 group and the oxygen atom of the boryl ligand, control the ortho-selectivity.

Palladium-catalyzed intermolecular transthioetherification of aryl halides with thioethers and thioesters

Functional group transfer reactions are an important synthetic tool in modern organic synthesis. Herein, we developed a new palladium-catalyzed intermolecular transthioetherification reaction of aryl halides with thioethers and thioesters. The synthetic utility and practicality of this catalytic protocol are demonstrated in a wide range of successful transformations (>70 examples). This catalytic protocol is applicable in carbonylative coupling processes as well, and the first example of carbonylative methylthioesterification of aryl halides has been achieved. Notably, this work also provides an approach to using natural products, such as methionine and selenomethionine, as the functional group sources.

Visible Light-Induced Borylation of C-O, C-N, and C-X Bonds

Boronic acids are centrally important functional motifs and synthetic precursors. Visible light-induced borylation may provide access to structurally diverse boronates, but a broadly efficient photocatalytic borylation method that can effect borylation of a wide range of substrates, including strong C-O bonds, remains elusive. Herein, we report a general, metal-free visible light-induced photocatalytic borylation platform that enables borylation of electron-rich derivatives of phenols and anilines, chloroarenes, as well as other haloarenes. The reaction exhibits excellent functional group tolerance, as demonstrated by the borylation of a range of structurally complex substrates. Remarkably, the reaction is catalyzed by phenothiazine, a simple organic photocatalyst with MW 200 that mediates the previously unachievable visible light-induced single electron reduction of phenol derivatives with reduction potentials as negative as approximately - 3 V versus SCE by a proton-coupled electron transfer mechanism. Mechanistic studies point to the crucial role of the photocatalyst-base interaction.

Generation of Organozinc Reagents from Arylsulfonium Salts Using a Nickel Catalyst and Zinc Dust

Readily available aryldimethylsulfonium triflates react with zinc powder under nickel catalysis via the selective cleavage of the sp2-hybridized carbon-sulfur bond to produce salt-free arylzinc triflates under mild conditions. This zincation displays superb chemoselectivity and thus represents a protocol that is complementary or orthogonal to existing methods. The generated arylzinc reagents show both high reactivity and chemoselectivity in palladium-catalyzed and copper-mediated cross-coupling reactions.

Copper-Photocatalyzed Borylation of Organic Halides under Batch and Continuous-Flow Conditions

The copper-photocatalyzed borylation of aryl, heteroaryl, vinyl and alkyl halides (I and Br) was reported. The reaction proceeded using a new heteroleptic Cu complex under irradiation with blue LEDs, giving the corresponding boronic-acid esters in good to excellent yields. The reaction was extended to continuous-flow conditions to allow an easy scale-up. The mechanism of the reaction was studied and a mechanism based on a reductive quenching (CuI/CuI*/Cu0) was suggested.

Photocatalyzed borylation using water-soluble quantum dots

The synthesis of arylboronates by Sandmeyer-type reactions in the presence of water still remains a significant challenge. Herein, we report the use of water-soluble MPA-capped quantum dot (QD) photocatalysts for the borylation of diazonium salts in the presence of water. A biphasic system under mild acidic conditions remains critical to prevent decomposition and competitive disulphide bond formation. The present protocol offers a broader scope of substrates and borylating agents. Additionally, this catalytic system offers a significantly high turnover number (TON). The present methodology can effectively distinguish subtle reactivity differences between boronic acids and boronates. Mechanistic investigation suggests an excited-state electron transfer pathway.

Copper-catalysed borylation of aryl chlorides

We report herein the first Cu-catalysed borylation of a wide range of aryl chlorides with different electronic and steric properties using a readily prepared NHC-stabilised Cu catalyst and KOtBu as the base with B2pin2 (pin = pinacolato) as the boron reagent. The aryl chlorides are converted into their corresponding arylboronic esters in good yields. The new procedure shows broad functional group tolerance, and B2neop2 (neop = neopentyl glycolato) can also be applied as the boron reagent.

Convenient and General Zinc-Catalyzed Borylation of Aryl Diazonium Salts and Aryltriazenes under Mild Conditions

A convenient and general zinc-catalyzed borylation of aryl diazonium salts and aryltriazenes has been developed. With bis- (pinacolato)diboron as the borylation reagent, aryldiazonium tetrafluoroborate salts and aryltriazenes were transformed into the corresponding arylboronates in moderate to excellent yields under mild conditions. As a convenient and practical methodology, no additional ligands, base, or any other additives are required here.

Palladium-Catalyzed Double Borylation of Diaryl Sulfoxides with Diboron

Borylation of the C-S bond of diaryl sulfoxides with bis(pinacolato)diboron (B 2 pin 2) is accomplished by means of a phosphine-ligated palladium catalyst and LiN(SiMe 3) 2 as a base. Both of the aryl rings of the diaryl sulfoxides are converted into borylated products.