1126-93-8Relevant academic research and scientific papers
La[N(SiMe3)2]3-Catalyzed Hydroboration of Esters and Other Challenging Unsaturated Groups
Kang, Zihan,Xu, Xiaojuan,Xue, Mingqiang,Yan, Dandan
, p. 1142 - 1146 (2019)
The commercially available homoleptic lanthanum amide La[N(SiMe3)2]3 (LaNTMS) is reported to enable the hydroboration of esters using pinacolborane (HBpin) as the reducing agent. A wide range of substrates inclu
Magnesium-catalyzed hydroboration of esters: Evidence for a new zwitterionic mechanism
Mukherjee, Debabrata,Ellern, Arkady,Sadow, Aaron D.
, p. 959 - 964 (2014)
A magnesium-catalyzed ester hydroboration reaction rapidly and efficiently (a pathway involving a zwitterionic alkoxyborate is proposed. The Royal Society of Chemistry 2014.
Palladium on carbon as an efficient, durable and economical catalyst for the alcoholysis of B2pin2
Li, Ning,Liu, Xiang,Meng, Xu,Shen, Jialu,Zhou, Junjie
, (2021)
Hydrogen has attracted much attention as one of the most promising chemical fuel candidates because of its zero emission during consumption. In order to solve the freezing problem of water based hydrolysis process, herein, the Pd/C as an efficient and stable catalyst for the methanolysis, ethanolysis, propanolysis and butanolysis of B2pin2 for the generation of hydrogen has been first developed. The large kinetic isotope effect (KIE) of kH/kD = 5.0, D2 formation from CD3OD and in situ tandem reaction have confirmed that alcohol is the only hydrogen source. Interestingly, the order of Ea of these alcohols in H2 evolution is MeOH (methanol, 29.57 kJ/mol) nBuOH (n-butanol, 41.98 kJ/mol), which is consistent with the known order of acidities of these alcohols (MeOH > EtOH > PrOH > nBuOH).
Green hydroboration of carboxylic acids and mechanism investigation
Wang, Weifan,Luo, Man,Zhu, Da,Yao, Weiwei,Xu, Li,Ma, Mengtao
, p. 3604 - 3608 (2019)
A catalyst-free and solvent-free method for the hydroboration of a variety of carboxylic acids with pinacolborane was developed. The hydroboration of various aromatic and aliphatic carboxylic acids as well as dicarboxylic acids with HBpin could be completed within 6 h at room temperature or within 1 h at 60 °C to give the products in quantitative yields under neat conditions without the need for any solvent or metal catalyst. The possible reaction mechanism was investigated in detail based on the corresponding DFT calculations and the stoichiometric reaction of acetic acid with different equivalents of HBpin (at room temperature and 0 °C) and it revealed the stepwise nature of the protocol.
Super hydride catalyzed ester and isocyanate hydroboration
Behera, Bedabyas,Ding, Yi,Du, Zonggang,Kumar, Arun
, (2021)
Commercially available, eco-friendly lithium triethylborohydride (LiHBEt3, Super hydride) was shown to be an excellent catalyst for the solvent-free hydroboration of esters using pinacolborane at ambient reaction conditions. This was achieved w
Catalytic Hydroboration of Esters by Versatile Thorium and Uranium Amide Complexes
Makarov, Konstantin,Kaushansky, Alexander,Eisen, Moris S.
, p. 273 - 284 (2022/01/03)
The challenging hydroboration of esters is achieved using simple uranium and thorium amides, U[N(SiMe3)2]3 and [(Me3Si)2N]2An[κ2-(N,C)-CH2Si(CH3)2N(SiMe3)] (An = Th or U) acting as precatalysts in the reaction with pinacolborane (HBpin). All three complexes showed impressive catalytic activities, reaching excellent yields. A large scope of esters was investigated including aliphatic, aromatic, and heterocyclic esters that were transformed cleanly to the corresponding hydroborated alcohols, which readily hydrolyzed to the free alcohols. Moreover, the actinide catalysts demonstrated unexpected high functional tolerance toward nitro, halide, cyano, and heteroaromatic functional groups. The reaction exhibited excellent selectivity toward the ester when additional double and triple unsaturated C-C bonds were present. Lactones and poly caprolactone have been successfully cleaved to the monomeric units, showing a great promise toward polymer degradation and recycling. Detailed kinetic studies are provided in order to determine the rate dependence on the concentration of catalyst, HBpin, and ester. A plausible mechanism is proposed based on stoichiometric reactions, DFT calculations, thermodynamic measurements, and deuterium-labeling studies.
N-Heterocyclic Carbene-Phosphinidenide Complexes as Hydroboration Catalysts
Bhattacharjee, Jayeeta,Bockfeld, Dirk,Tamm, Matthias
supporting information, p. 1098 - 1109 (2022/01/27)
The reactions of the N-heterocyclic carbene-phosphinidene adducts (NHC)PSiMe3 and (NHC)PH with the dinuclear ruthenium and osmium complexes [(η6-p-cymene)MCl2]2 (M = Ru, Os) afforded the half-sandwich complexes
Synthesis and characterization of rare-earth metallate amido complexes bearing the 2-amidate-functionalized indolyl ligand and their application in the hydroboration of esters with pinacolborane
Bao, Qin,Gao, Jianjian,Hong, Dongjing,Mu, Xiaolong,Song, Lulu,Wang, Shaowu,Wei, Yun,Zhou, Shuangliu,Zhu, Xiancui
, p. 2953 - 2961 (2022/02/21)
The reactions of 2-amidate-functionalized indolyl proligand 2-(2,6-iPr2C6H3NHCO)C8H5NH (H2L) with [(Me3Si)2N]3RE(μ-Cl)Li(THF)3 were studied leading to the synthesis and characterization of a series of novel discrete trinuclear rare-earth metallate amido complexes containing the anion [{η1:(μ2-η1:η1):η1-LREN(SiMe3)2}3(μ3-Cl)]? and cation Li+(THF)4 (RE = Y(1a), Nd (1b), Sm (1c), Gd (1d), Dy (1e), Er (1f), and Yb (1g)) in good yields by silylamine elimination. All of the complexes were characterized by spectroscopic methods, elemental analyses and single-crystal X-ray diffraction, and complexes 1a and 1c were additionally characterized by NMR spectroscopy. As proof of principle of their activity, these complexes were used as precatalysts for the hydroboration of esters using HBpin as the hydride source displaying high activity under neat and room temperature conditions. As a result, the ligand, ionic and multinuclear cooperative effects on catalytic activity were observed.
Hydroborative reduction of amides to amines mediated by La(CH2C6H4NMe2-: O)3
Gong, Mingliang,Guo, Chenjun,Luo, Yunjie,Xie, Hongzhen,Zhang, Fangcao
, p. 779 - 791 (2022/01/22)
The deoxygenative reduction of amides to amines is a great challenge for resonance-stabilized carboxamide moieties, although this synthetic strategy is an attractive approach to access the corresponding amines. La(CH2C6H4NMe2-o)3, a simple and easily accessible lanthanide complex, was found to be highly efficient not only for secondary and tertiary amide reduction, but also for the most challenging primary reduction with pinacolborane. This protocol exhibited good tolerance for many functional groups and heteroatoms, and could be applied to gram-scale synthesis. The active species in this catalytic cycle was likely a lanthanide hydride.
Hydroboration of nitriles, esters, and amides catalyzed by simple neosilyllithium
Bandyopadhyay, Ayan,Bhattacharjee, Jayeeta,Kumar Singh, Saurabh,Kumari, Kusum,Moorthy, Shruti,Panda, Tarun K.,Sai Kumar, Gobbilla
supporting information, (2022/03/31)
We present here an efficient method for the hydroboration of organic nitriles, carboxylic esters, and carboxamides with pinacolborane (HBpin) using an alkali metal catalyst, neosilyllithium (LiCH2SiMe3), in neat reaction conditions. The reactions were accomplished with efficient catalytic reactivity and demonstrated by neosilyllithium at room temperature, in solvent-free condition, to afford a high yield of the corresponding N-boryl amines, boryl ethers, and amine hydrochlorides. The protocol for the catalytic reaction presented in this paper is simple and efficient, with diverse substrate scope for nitriles, carboxylic esters, and carboxamides showing excellent functional group tolerance. DLPNO-CCSD(T) calculations were also performed, showing that the hydroboration of nitriles catalyzed by neosilyllithium occurs through the pre-coordination of the nitrile at Lewis acid lithium followed by hydride migration from the B–H entity.
