5123-13-7

Basic information

• Product Name: (5,5-DIMETHYL-1,3,2-DIOXABORINAN-2-YL)BENZENE
• Synonyms: Phenylboronic acid neopentylglycol ester,(5,5-Dimethyl-2-phenyl-1,3,2-dioxaborinane, Phenyl boronic acid neopentylglycol ester;Phenylboronic acid neopentylglycol ester 97%;PHENYLBORONIC ACID, NEOPENTYL ESTER;5,5-DIMETHYL-2-PHENYL-1,3,2-DIOXABORINANE;(5,5-DIMETHYL-1,3,2-DIOXABORINAN-2-YL)BENZENE;Phenylboronic acid neopentylglycol ester, 97%;Phenylboronic Acid, neopentyl glycol cyclic ester;(5,5-Dimethyl-2-phenyl-1,3,2-dioxaborinane, Phenyl boronic acid neopentylglycol ester
• CAS NO: 5123-13-7
• Molecular Formula: C₁₁H₁₅BO₂
• Molecular Weight: 190.05
• Mol File: 5123-13-7.mol

Chemical Properties

• Melting Point: 62-66 °C(lit.)
• Boiling Point: 287.761°C at 760 mmHg
• Flash Point: 127.834°C
• Appearance: /
• Density: 1.008g/cm³
• Vapor Pressure: 0.004mmHg at 25°C
• Refractive Index: 1.493
• Storage Temp.: 2-8°C
• Solubility: soluble in Methanol
• CAS DataBase Reference: (5,5-DIMETHYL-1,3,2-DIOXABORINAN-2-YL)BENZENE(CAS DataBase Reference)
• NIST Chemistry Reference: (5,5-DIMETHYL-1,3,2-DIOXABORINAN-2-YL)BENZENE(5123-13-7)
• EPA Substance Registry System: (5,5-DIMETHYL-1,3,2-DIOXABORINAN-2-YL)BENZENE(5123-13-7)

Safety Data

• Hazard Codes: Xi
• Statements: 36/37/38
• Safety Statements: 26-36/37
• WGK Germany: 3
• Hazardous Substances Data: 5123-13-7(Hazardous Substances Data)

Usage

Uses

Used in Pharmaceutical Industry:
(5,5-DIMETHYL-1,3,2-DIOXABORINAN-2-YL)BENZENE is used as a key intermediate in the synthesis of pharmaceuticals for its ability to form stable covalent bonds with biologically active molecules, contributing to the development of new drugs with enhanced efficacy and selectivity.
Used in Agrochemical Industry:
In the agrochemical sector, (5,5-DIMETHYL-1,3,2-DIOXABORINAN-2-YL)BENZENE is utilized as a building block in the creation of novel agrochemicals, such as pesticides and herbicides, where its strong bonding capabilities can improve the performance and selectivity of these compounds towards target organisms.
Used in Materials Science:
(5,5-DIMETHYL-1,3,2-DIOXABORINAN-2-YL)BENZENE is employed in materials science as a component in the design of advanced materials, leveraging its bonding properties to enhance the mechanical, thermal, or electrical properties of the resulting materials.
Used in Catalysis:
In the field of catalysis, (5,5-DIMETHYL-1,3,2-DIOXABORINAN-2-YL)BENZENE is used to modify catalysts, potentially improving their activity, selectivity, and stability by forming strong bonds with reaction intermediates or by stabilizing catalytically active species.

InChI:InChI=1/C11H15BO2/c1-11(2)8-13-12(14-9-11)10-6-4-3-5-7-10/h3-7H,8-9H2,1-2H3

Upstream product

• 3262-89-3 triphenylboroxine 
• 126-30-7 2,2-Dimethyl-1,3-propanediol 
• 2848-16-0 diphenyldiboronic acid 
• 98-80-6 phenylboronic acid 
• 17763-67-6 Phenyl triflate 
• 201733-56-4 2-(5,5-dimethyl-1,3,2-dioxaborinan-2-yl)-5,5-dimethyl-1,3,2-dioxaborinane 
• 1692-26-8 bis(propan-2-yl) phenylboronate 
• 4406-72-8 2-phenyl[1,3,2]dioxaborolane 
• 603-36-1 triphenylantimony 
• 5035-52-9 dichlorophenylstibine 
• 2629-47-2 diphenylantimony(III) chloride 
• 603-33-8 triphenylbismuthane 
• 24388-23-6 2-phenyl-4,4,5,5-tetramethyl-1,3,2-dioxoborole 
• 1061180-99-1 (4R,5R)-diisopropyl-2-phenyl-1,3,2-dioxaborolane-4,5-dicarboxylate 

Downstream Products

• 100-51-6 benzyl alcohol 
• 108478-28-0 methyl 6-methoxybiphenyl-3-carboxylate 
• 220616-20-6 1,4-diphenylpiperidine 
• 62787-21-7 3,5-di-tert-butylphenyl phenyl ether 
• 92-52-4 biphenyl 
• 14990-09-1 tert-butyl cinnamate 
• 591-50-4 iodobenzene 
• 70720-38-6 benzyl-(3-methyl-2-pyridinyl)amine 
• 59310-32-6 1-(3-phenylnaphthalen-2-yl)ethanone 

Relevant articles and documents

Photochemical and electrochemical C-N borylation of arylhydrazines

The C-N borylation of arylhydrazine hydrochlorides with bis(pinacolato)diboron was achieved under photochemical and electrochemical conditions, respectively. This novel and scalable transformation provides two efficient and mild transition-metal-free synt

Unreactive C-N Bond Activation of Anilines via Photoinduced Aerobic Borylation

Unreactive C-N bond activation of anilines was achieved by photoinduced aerobic borylation. A diverse range of tertiary and secondary anilines were converted to aryl boronate esters in moderate to good yields with wide functional group tolerance under simple and ambient photochemical conditions. This transformation achieved the direct and facile C-N bond activation of unreactive anilines, providing a convenient and practical route transforming widely available anilines into useful aryl boronate esters.

Synthesis of arylboronates via the Pd-catalyzed desulfitative coupling reaction of sodium arylsulfinates with bis(pinacolato)diboron

The desulfitative borylation reaction of sodium arylsulfinates with bis(pinacolato)diboron or bis(neopentylglycolato)diboron under palladium catalysis has been developed, allowing selective C-B bond formation to give arylboronates with a range of functional groups in moderate to good yields under mild reaction conditions. A gram-scale preparation as well as the cascade Suzuki-Miyaura cross-coupling of arylboronates demonstrated the potential practical utility in organic synthesis.

Selective C-O Bond Reduction and Borylation of Aryl Ethers Catalyzed by a Rhodium-Aluminum Heterobimetallic Complex

We report the catalytic reduction of a C-O bond and the borylation by a rhodium complex bearing an X-Type PAlP pincer ligand. We have revealed the reaction mechanism based on the characterization of the reaction intermediate and deuterium-labeling experiments. Notably, this novel catalytic system shows steric-hindrance-dependent chemoselectivity that is distinct from conventional Ni-based catalysts and suggests a new strategy for selective C-O bond activation by heterobimetallic catalysis.

Ni-Catalyzed Borylation of Aryl Sulfoxides

A nickel/N-heterocyclic carbene (NHC) catalytic system has been developed for the borylation of aryl sulfoxides with B2(neop)2 (neop=neopentyl glycolato). A wide range of aryl sulfoxides with different electronic and steric properties were converted into the corresponding arylboronic esters in good yields. The regioselective borylation of unsymmetric diaryl sulfoxides was also feasible leading to borylation of the sterically less encumbered aryl substituent. Competition experiments demonstrated that an electron-deficient aryl moiety reacts preferentially. The origin of the selectivity in the Ni-catalyzed borylation of electronically biased unsymmetrical diaryl sulfoxide lies in the oxidative addition step of the catalytic cycle, as oxidative addition of methoxyphenyl 4-(trifluoromethyl)phenyl sulfoxide to the Ni(0) complex occurs selectively to give the structurally characterized complex trans-[Ni(ICy)2(4-CF3-C6H4){(SO)-4-MeO-C6H4}] 4. For complex 5, the isomer trans-[Ni(ICy)2(C6H5)(OSC6H5)] 5-I was structurally characterized in which the phenyl sulfinyl ligand is bound via the oxygen atom to nickel. In solution, the complex trans-[Ni(ICy)2(C6H5)(OSC6H5)] 5-I is in equilibrium with the S-bonded isomer trans-[Ni(ICy)2(C6H5)(SOC6H5)] 5, as shown by NMR spectroscopy. DFT calculations reveal that these isomers are separated by a mere 0.3 kJ/mol (M06/def2-TZVP-level of theory) and connected via a transition state trans-[Ni(ICy)2(C6H5)(η2-{SO}-C6H5)], which lies only 10.8 kcal/mol above 5.

Cobalt-Catalyzed C(sp2)-C(sp3) Suzuki-Miyaura Cross Coupling

A cobalt-catalyzed method for the C(sp2)-C(sp3) Suzuki-Miyaura cross coupling of aryl boronic esters and alkyl bromides is described. Cobalt-ligand combinations were assayed with high-throughput experimentation, and cobalt(II) sources with trans-N,N′-dimethylcyclohexane-1,2-diamine (DMCyDA, L1) produced optimal yield and selectivity. The scope of this transformation encompassed steric and electronic diversity on the aryl boronate nucleophile as well as various levels of branching and synthetically valuable functionality on the electrophile. Radical trap experiments support the formation of electrophile-derived radicals during catalysis.

Nickel-Catalyzed Regioselective Alkenylarylation of γ,δ-Alkenyl Ketones via Carbonyl Coordination

We disclose a nickel-catalyzed reaction, which enabled us to difunctionalize unactivated γ,δ-alkenes in ketones with alkenyl triflates and arylboronic esters. The reaction was made feasible by the use of 5-chloro-8-hydroxyquinoline as a ligand along with

Visible-Light-Induced Ni-Catalyzed Radical Borylation of Chloroarenes

A highly selective and general photoinduced C-Cl borylation protocol that employs [Ni(IMes)2] (IMes = 1,3-dimesitylimidazoline-2-ylidene) for the radical borylation of chloroarenes is reported. This photoinduced system operates with visible light (400 nm) and achieves borylation of a wide range of chloroarenes with B2pin2 at room temperature in excellent yields and with high selectivity, thereby demonstrating its broad utility and functional group tolerance. Mechanistic investigations suggest that the borylation reactions proceed via a radical process. EPR studies demonstrate that [Ni(IMes)2] undergoes very fast chlorine atom abstraction from aryl chlorides to give [NiI(IMes)2Cl] and aryl radicals. Control experiments indicate that light promotes the reaction of [NiI(IMes)2Cl] with aryl chlorides generating additional aryl radicals and [NiII(IMes)2Cl2]. The aryl radicals react with an anionic sp2-sp3 diborane [B2pin2(OMe)]- formed from B2pin2 and KOMe to yield the corresponding borylation product and the [Bpin(OMe)]?- radical anion, which reduces [NiII(IMes)2Cl2] under irradiation to regenerate [NiI(IMes)2Cl] and [Ni(IMes)2] for the next catalytic cycle.

Small Phosphine Ligands Enable Selective Oxidative Addition of Ar-O over Ar-Cl Bonds at Nickel(0)

Current methods for Suzuki-Miyaura couplings of nontriflate phenol derivatives are limited by their intolerance of halides including aryl chlorides. This is because Ni(0) and Pd(0) often undergo oxidative addition of organohalides at a similar or faster rate than most Ar-O bonds. DFT and stoichiometric oxidative addition studies demonstrate that small phosphines, in particular PMe3, are unique in promoting preferential reaction of Ni(0) with aryl tosylates and other C-O bonds in the presence of aryl chlorides. This selectivity was exploited in the first Ni-catalyzed C-O-selective Suzuki-Miyaura coupling of chlorinated phenol derivatives where the oxygen-containing leaving group is not a fluorinated sulfonate such as triflate. Computational studies suggest that the origin of divergent selectivity between PMe3 and other phosphines differs from prior examples of ligand-controlled chemodivergent cross-couplings. PMe3 effects selective reaction at tosylate due to both electronic and steric factors. A close interaction between nickel and a sulfonyl oxygen of tosylate during oxidative addition is critical to the observed selectivity.

Rh-Catalyzed Base-Free Decarbonylative Borylation of Twisted Amides

We report the rhodium-catalyzed base-free decarbonylative borylation of twisted amides. The synthesis of versatile arylboronate esters from aryl twisted amides is achieved via decarbonylative rhodium(I) catalysis and highly selective N-C(O) insertion. The method is notable for a very practical, additive-free Rh(I) catalyst system. The method shows broad functional group tolerance and excellent substrate scope, including site-selective decarbonylative borylation/Heck cross-coupling via divergent N-C/C-Br cleavage and late-stage pharmaceutical borylation.