3602-36-6

Upstream product

• 130970-82-0 S-catecholboryl (N,N-dimethylaminomethyl)phenyldithiophosphinate 
• 1111-72-4 carbon dioxide 
• 274-07-7 benzo[1,3,2]dioxaborole 
• 124-38-9 carbon dioxide 
• 1318802-31-1 C₂₀H₂₀BO₂P 
• 1250258-94-6 [2-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)phenyl]diphenylphosphine 
• 1250439-06-5 C₆H₄(P(C₆H₅)2)(B(OCH₂)2C(CH₃)2) 
• 372-46-3 fluorocyclohexane 
• 109-99-9 tetrahydrofuran 
• 55718-76-8 2-chloro-1,3,2-benzodioxaborole 
• 1353585-07-5 N-(benzo[d][1,3,2]dioxaborol-2-yl)-N-benzylbenzo[d][1,3,2]dioxaborol-2-amine 
• 100-52-7 benzaldehyde 
• 100-17-4 para-methoxynitrobenzene 

Downstream Products

• 274-07-7 benzo[1,3,2]dioxaborole 
• 858865-56-2 [bis(triphenylphosphoranylidene)ammonium][(catBOBcat)*(OAc)] 

Relevant academic research and scientific papers

Uranyl Functionalization Mediated by Redox-Active Ligands: Generation of O-C Bonds via Acylation

A series of uranyl compounds with the redox-active iminoquinone ligand have been synthesized, and their electronic structures elucidated using multinuclear NMR, EPR, electronic absorption spectroscopies, SQUID magnetometry, and X-ray crystallography. Characterization and analysis of the iminoquinone (iq0) complex, (dippiq)UO2(OTf)2THF (1-iq), the iminosemiquinone (isq1-) complex, (dippisq)2UO2THF (2-isq), and the amidophenolate (ap2-) complex, [(dippap)2UO2THF][K(18-crown-6)(THF)2]2(3-ap crown) show that reduction events are ligand-based, with the uranium center remaining in the hexavalent state. Reactivity of 2-isq with B-chlorocatecholborane or pivaloyl chloride leads to U-Ouranyl bond scission and reduction of U(VI) to U(IV) concomitant with ligand oxidation along with organic byproducts. 18O isotopic labeling experiments along with IR spectroscopy, mass spectrometry, and multinuclear NMR spectroscopy confirm that the organic byproducts contain oxygen atoms which originate from U-Ouranyl bond activation.

Interactions of C?F Bonds with Hydridoboranes: Reduction, Borylation and Friedel–Crafts Alkylation

The stoichiometric reactions of the alkylfluorides 1-fluoroadamantane (Ad-F), fluorocyclohexane (Cy-F), 1-fluoropentane (Pent-F) and benzyl fluorides with secondary boranes pinacolborane (HBpin), catecholborane (HBcat), 9-borabicyclo(3.3.1)nonane (9-BBN)

Imido-hydrido complexes of Mo(IV): Catalysis and mechanistic aspects of hydroboration reactions

Imido-hydrido complexes (ArN)Mo(H)(Cl)(PMe3)3 (1) and (ArN)Mo(H)2(PMe3)3 (2) (Ar = 2,6-diisopropylphenyl) catalyse a variety of hydroboration reactions, including the rare examples of addition of HBCat to nitriles to form bis(borylated) amines RCH2N(BCat)2. Stoichiometric reactivity of complexes 1 and 2 with nitriles and HBCat suggest that catalytic reactions proceed via a series of agostic borylamido and borylamino complexes. For complex 1, catalysis starts with addition of nitriles across the Mo-H bond to give (ArN)Mo(Cl)(NCHR)(PMe3)2; whereas for complex 2 stoichiometric reactions suggest initial addition of HBCat to form the agostic complex Mo(H)2(PMe3)3(η3-NAr-HBcat) (16).

Hydroboration of Carbon Dioxide Using Ambiphilic Phosphine-Borane Catalysts: On the Role of the Formaldehyde Adduct

Ambiphilic phosphine-borane derivatives 1-B(OR)2-2-PR′2-C6H4 (R′ = Ph (1), iPr (2); (OR)2 = (OMe)2 (1a, 2a); catechol (1b, 2b) pinacol (1c, 2c), -OCH2C-(CH3)2CH2O- (1d)) were tested as catalysts for the hydroboration of CO2 using HBcat or BH3·SMe2 to generate methoxyboranes. It was shown that the most active species were the catechol derivatives 1b and 2b. In the presence of HBcat, without CO2, ambiphilic species 1a, 1c, and 1d were shown to transform to 1b, whereas 2a and 2c were shown to transform to 2b. The formaldehyde adducts 1b·CH2O and 2b·CH2O are postulated to be the active catalysts in the reduction of CO2 rather than being simple resting states. Isotope labeling experiments and density functional theory (DFT) studies show that once the formaldehyde adduct is generated, the CH2O moiety remains on the ambiphilic system through catalysis. Species 2b·CH2O was shown to exhibit turnover frequencies for the CO2 reduction using BH3·SMe2 up to 228 h-1 at ambient temperature and up to 873 h-1 at 70 °C, mirroring the catalytic activity of 1b. (Figure Presented)

An efficient nickel catalyst for the reduction of carbon dioxide with a borane

Nickel hydride with a diphosphinite-based ligand catalyzes the highly efficient reduction of CO2 with catecholborane, and the hydrolysis of the resulting methoxyboryl species produces CH3OH in good yield. The mechanism involves a nickel formate, formaldehyde, and a nickel methoxide as different reduced stages for CO2. The reaction may also be catalyzed by an air-stable nickel formate.

Highly enantioselective oxazaborolidine-catalyzed reduction of 1,3-dicarbonyl compounds: Role of the additive diethylaniline

The oxazaborolidine-catalyzed reduction of 2,2-disubstituted cycloalkan-1,3-diones or hindered 2,2-disubstituted cyclic ketones using catecholborane as reductant proceeds with greater enantioselectivity when N,N-diethylaniline is added. It has now been sh

Catalyzed hydroboration of nitrostyrenes and 4-vinylaniline: A mild and selective route to aniline derivatives containing boronate esters

Transition metal catalyzed reactions of catecholborane (HBcat; cat = 1,2-O2C6H4) with β-nitrostyrene and 3-nitrostyrene lead to products derived from competing hydrogenation and hydroboration of the alkene unit along with reduction of the nitro group. Hydroboration of 4-vinylaniline gave regioselective formation of either the branched or the linear organoboronate ester depending upon the catalyst precursors (i.e., RhCl(PPh3)3 or Rh(acac)(dppe) vs [Cp*IrCl2]2) used to facilitate this reaction. Hydroboration products were converted to air-stable primary amines by addition of pinacol.

C-H Activation and Functionalization of Unsaturated Hydrocarbons by Transition-Metal Boryl Complexes

Transition-metal boryl complexes of the form Cp′Fe(CO)LBcat and (CO)5MBcat, where Cp′ = C5H5, C5Me5, M = Mn, Re, L = CO, PMe3, and cat = 1,2-O2C6H4, were synthesized by reaction of ClBcat with [Cp′Fe(CO)L]- or [M(CO)5]-. X-ray crystal structures of CpFe-(CO)2Bcat, Cp*Fe(CO)2Bcat, and (CO)5MnBcat were obtained. Upon irradiation, these metal boryl complexes reacted with arenes and alkenes to form aryl- and vinylboronate ester products in moderate to high yields. Monosubstituted arenes with methyl, chloro, trifluoromethyl, methoxy, and dimethylamino substituents were used as substrates, and the resulting ratios of ortho- to meta- to para-substituted arene products were measured. No significant electronic effects were observed, indicating that the chemistry is not occurring through a typical electrophilic aromatic substitution pathway. Competition experiments between toluene and other substituted arenes were conducted. Reactivity differences were small, but anisole was found to have the fastest rate of reaction. Kinetic isotope effects were measured for the reaction of CpFe(CO)2Bcat, (CO)5MnBcat, or (CO)5ReBcat with benzene/ benzene-d6 mixtures and were found to be 3.3 ± 0.4, 2.1 ± 0.1, and 5.4 ± 0.4, respectively. This difference in isotope effect along with differences in selectivities with substituted arsenic reagents rules out a mechanism by which a common free Beat radical attacks free substrate. Several experiments were also conducted to probe for CO loss. A 13CO-labeling experiment, CO inhibition experiment, and PMe3 trapping experiment indicate that the mechanism most likely proceeds through irreversible CO loss to form a 16-electron intermediate. Functionalization of alkenes to form vinylboronate esters was also observed, and mechanistic studies showed the absence of a measurable kinetic isotope effect for reaction of CpFe(CO)2Bcat or (CO)5ReBcat with ethylene/ethylene-d4 mixtures or for reaction with ethylene-d2.

SYNTHESIS OF S-CATECHOLBORYL (N,N-DIMETHYLAMINOMETHYL)PHENYLDITHIOPHOSPHINATE

S-Catecholboryl (N,N-dimethylaminomethyl)phenyldithiophosphinate, the first representative of S-diorganylboric derivatives of phosphonous acid was obtained by the reaction of catecholboryl (N,N-dimethylaminomethyl)phenylphosphine with sulfur.