10221-56-4

Upstream product

• 73183-34-3 bis(pinacol)diborane 
• 71-43-2 benzene 
• 1111-72-4 carbon dioxide 
• 4630-82-4 methyl cyclohexylcarboxylate 
• 83947-62-0 pinacol lithio(trimethylsilyl)methaneboronate 
• 1038-95-5 Tri(p-tolyl)phosphine 
• 25015-63-8 4,4,5,5-tetramethyl-[1,3,2]-dioxaboralane 
• 110-83-8 cyclohexene 
• 64-18-6 formic acid 
• 112320-11-3 RuH₂(H₂)2(tricyclohexylphosphine)2 
• 873204-27-4 dihydridobis(η2-dihydrogen)bis(tricyclopentylphosphine)ruthenium(II) 
• 24544-04-5 2,6-diisopropylbenzenamine 
• 1354969-56-4 catalytic reaction of aldehydes and ketones with HBpin: general procedure 
• 93-58-3 benzoic acid methyl ester 

Downstream Products

• 1602924-48-0 C₁₅H₂₃BO₃Si 
• 82172-54-1 triphenyl((4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)oxy)silane 
• 1602924-55-9 C₂₄H₂₇BO₂⁽¹⁸⁾OSi 
• 1602924-47-9 C₁₉H₂₅BO₃Si 
• 1349697-23-9 dimethyl(phenyl)((4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)oxy)silane 
• 375853-82-0 tert-Butyl 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-3,6-dihydro-1(2H)-pyridinecarboxylate 
• 760992-14-1 1-[bis(4-methoxyphenyl)methyl]-6,7-dimethoxy-3-[4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]-1,4-dihydroindeno[1,2-c]pyrazole 

Relevant academic research and scientific papers

Cobalt catalysed reduction of CO2via hydroboration

We report an operationally convenient reduction of CO2 to methanol via cobalt catalysed hydroboration which occurs under mild reaction conditions. Addition of NaHBEt3 to Co(acac)3 generates an active hydroboration catalyst, which is proposed to be a “Co-H” species on the basis of infrared spectroscopy. The reduction of CO2 in the presence of various boranes showed that BH3·SMe2 afforded near quantitative conversion (98% NMR yield) to methanol upon hydrolysis.

Borane-mediated carbon dioxide reduction at ruthenium: Formation of C 1 and C2 compounds

One and two: The C2 compound pinBOCH2OCHO (see scheme; HBpin=pinacolborane) and several C1 compounds have been obtained from the borane-mediated reduction of CO2 under mild conditions with the catalyst precursor [RuH2(H2) 2(PCy3)2]. Mechanistic investigation highlights the role of a series of new carbonyl ruthenium complexes that were characterized by multinuclear NMR spectroscopy, IR spectroscopy, and X-ray diffraction studies. Copyright

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.

A N-Phosphinoamidinato NHC-Diborene Catalyst for Hydroboration

The use of the N-phosphinoamidinato NHC-diborene catalyst 2 for hydroboration is described. The N-phosphinoamidine tBu2PN(H)C(Ph)= N(2,6-iPr2C6H3) was reacted with nBuLi in Et2O to afford the lithium derivative, which was then treated with B2Br4(SMe2)2 in toluene to form the N-phosphinoamidinate-bridged diborane 1. It was reacted with the N-heterocyclic carbene IMe (:C{N(CH3)C(CH3)}2) and excess potassium graphite at room temperature in toluene to give the N-phosphinoamidinato NHC-diborene compound 2. It can stoichiometrically activate ammonia-borane and carbon dioxide. It also showed catalytic capability. A 2 mol % portion of 2 catalyzed the hydroboration of carbon dioxide (CO2) with pinacolborane (HBpin) in deuterated benzene (C6D6) at 110 °C (conversion >99%), which afforded the methoxyborane [pinBOMe] (yield 97.8%, TOF 33.3 h-1) and the bis(boryl) oxide [(pinB)2O]. In addition, 5 mol % of 2 catalyzed the N-formylation of secondary and primary amines by carbon dioxide and pinacolborane to yield the N-formamides (average yield 91.6%, TOF 25.9 h-1). Moreover, 2 showed chemoselectivity toward catalytic hydroboration of carbonyl compounds. In mechanistic studies, the B= B double bond in compound 2 activated the substrates, the intermediates of which then underwent hydroboration with pinacolborane to yield the products and regenerate catalyst 2.

Cooperative bond activation and catalytic reduction of carbon dioxide at a group 13 metal center

A single-component ambiphilic system capable of the cooperative activation of protic, hydridic and apolar H-X bonds across a Group 13 metal/activated β-diketiminato (Nacnac) ligand framework is reported. The hydride complex derived from the activation of H2 is shown to be a competent catalyst for the highly selective reduction of CO2 to a methanol derivative. To our knowledge, this process represents the first example of a reduction process of this type catalyzed by a molecular gallium complex. A single-component ambiphilic Group 13 system has been developed, capable of the cooperative activation of protic, hydridic, and apolar H-X bonds. The hydride complex derived from the activation of H2 catalyzes the selective transformation of CO2 to a methanol derivative, representing the first example of such a reduction process catalyzed by a molecular gallium complex.

Expedient Hydrofunctionalisation of Carbonyls and Imines Initiated by Phosphacyclohexadienyl Anions

The ability of phosphacyclohexadienyl anions [Li(1-R-PC5Ph3H2)] [R=Me (1 a), nBu (1 b), tBu (1 c), Ph (1 d) and CH2SiMe3 (1 e)] to initiate hydrofunctionalisation reactions was investigated and compar

Zinc hydridotriphenylborates supported by a neutral macrocyclic polyamine

The zinc hydridotriphenylborates [(L)Zn(TMDS)][HBPh3] and [(L)ZnX][HBPh3] (L = Me4TACD, Me4[12]aneN4; TMDS = N(SiHMe2)2; X = Cl, Br, I) were synthesized by BPh3-mediated β-SiH abstraction and salt metathesis with KHBPh3, respectively. CO2 is rapidly inserted into the B-H bonds. [(L)Zn(TMDS)][HBPh3] catalyzes the hydroboration of polar substrates including CO2.

Aromaticity as stabilizing element in the bidentate activation for the catalytic reduction of carbon dioxide

A new transition-metal-free mode for the catalytic reduction of carbon dioxide via bidentate interaction has been developed. In the presence of Li2[1,2-C6H4(BH3)2], CO2 can be selectively transformed to either methane or methanol, depending on the reducing agent. The bidentate nature of binding is supported by X-ray analysis of an intermediate analogue, which experiences special stabilization due to aromatic character in the bidentate interaction. Kinetic studies revealed a first-order reaction rate. The transformation can be conducted without any solvent.

Acetate-catalyzed hydroboration of CO2 for the selective formation of methanol-equivalent products

The present study details the use of the acetate anion, an inexpensive and robust anion, as a CO2 hydroboration catalyst for the selective formation, in most cases, of methanol-equivalent borane products. Thus, upon heating (90 °C, PhBr), tetrabutylammonium, sodium and potassium acetate (1, 2 and 3, respectively) effectively catalyze CO2 hydroboration by pinacolborane (pinB-H) to afford CO2 reduction products HOCOBpin (A), pinBOCH2OBpin (B) and methoxyborane (C). In most cases, high selectivity for product C with higher borane loading and longer reaction time with a TON of up to 970 was observed. The reduction catalysis remains efficient at low catalyst loading (down to 0.1 mol%) and may also be performed under solvent-free conditions using salt 1 as a catalyst, reflecting the excellent robustness and stability of the acetate anion. In control experiments, a 1/1 1/pinB-H mixture was found to react fast with CO2 at room temperature to produce formate species [pinB(O2CH)(OAc)][N(nBu)4] (5) through CO2 insertion into the B-H bond. DFT calculations were also performed to gain insight into the acetate-mediated CO2 hydroboration catalysis, which further supported the crucial role of acetate as a Lewis base in CO2 functionalization catalysis by pinB-H. The DFT-estimated mechanism is in line with experimental data and rationalizes the formation of the most thermodynamically stable reduction product C through acetate catalysis.

Hydrolysis of B2pin2 over Pd/C Catalyst: High Efficiency, Mechanism, and in situ Tandem Reaction

A facile and effective synthesis of H2 or D2 from Pd/C catalyzed hydrolysis of B2pin2 has first been developed. Among them, B2pin2 is frequently used for borylation reaction, and has rarely been used for hydrogen evolution. The kinetic isotope effects (KIEs) and tandem reaction for diphenylacetylene and norbornene hydrogenation have confirmed both two H atoms of H2 gas are provided from H2O. This is contrary to other boron compounds hydrolysis (including NH3BH3, NaBH4), which generates H2 with only one H atom provided by water and the other one by boron compounds. Note that the hydrolysis of B2pin2 in D2O also provides an easy and useful synthesis of D2.