1143018-72-7

Basic information

• Product Name: 4,4,5,5-tetramethyl-2-(1-phenylethoxy)-1,3,2-dioxaborolane
• Synonyms: 4,4,5,5-tetramethyl-2-(1-phenylethoxy)-1,3,2-dioxaborolane
• CAS NO: 1143018-72-7
• Molecular Weight: 248.13
• Mol File: 1143018-72-7.mol
• Article Data: 104

Chemical Properties

• CAS DataBase Reference: 4,4,5,5-tetramethyl-2-(1-phenylethoxy)-1,3,2-dioxaborolane(CAS DataBase Reference)
• NIST Chemistry Reference: 4,4,5,5-tetramethyl-2-(1-phenylethoxy)-1,3,2-dioxaborolane(1143018-72-7)
• EPA Substance Registry System: 4,4,5,5-tetramethyl-2-(1-phenylethoxy)-1,3,2-dioxaborolane(1143018-72-7)

Safety Data

• Hazardous Substances Data: 1143018-72-7(Hazardous Substances Data)

Upstream product

• 100-52-7 benzaldehyde 
• 98-86-2 acetophenone 
• 25015-63-8 4,4,5,5-tetramethyl-[1,3,2]-dioxaboralane 
• 96-09-3 styrene oxide 
• 73183-34-3 bis(pinacol)diborane 

Downstream Products

• 1445-91-6 (S)-1-phenylethanol 
• 1517-69-7 (R)-1-phenylethanol 
• 98-85-1 1-Phenylethanol 

Relevant articles and documents

N-Heterocyclic Carbene-Stabilized Germanium and Tin Analogues of Heavier Nitriles: Synthesis, Reactivity, and Catalytic Application

The synthesis of stable heavier analogues of nitriles as monomeric tetrylene-phosphinidenes MesTerEP(IDipp) (E = Ge, Sn; MesTer = 2,6-Mes2C6H3, IDipp = C([N-(2,6-iPr2C6H4)CH]2) was achieved by taking advantage of NHC (N-heterocyclic carbene, here IDipp) coordination to the low-valent phosphorus center. Multiple bonding character of the E-P bonds was examined experimentally and computationally. Both germanium and tin compounds undergo [2+2] cycloaddition with diphenylketene, whereas reaction of the tin derivative with tris(pentafluorophenyl)borane provided unique "push-pull" phosphastannene (MesTer)(Ar)Sn = P(IDipp) (Ar = C6F4[B(F)(C6F5)2]). Going further, we demonstrated the potential of tetrylene-phosphinidene complexes in catalytic hydroboration of carbonyl compounds.

Ligand Effects in Calcium Catalyzed Ketone Hydroboration

The first “naked” (Lewis base-free) cationic Ca amidinate complex [tBuAmDIPPCa(C6H6)]+[B(C6F5)4]– was prepared in 62 % yield {tBuAmDIPP = tBuC(N–

Ni(bpy)(cod): A Convenient Entryway into the Efficient Hydroboration of Ketones, Aldehydes, and Imines

The catalytic hydroboration of ketones, aldehydes, and imines with pinacol borane and Ni(bpy)(cod) has been demonstrated in benzene at room temperature and low catalyst loadings (0.03-0.3 mol-%). Spectroscopic and structural evidence support the formulati

Supported Single-Site Ti(IV) on a Metal-Organic Framework for the Hydroboration of Carbonyl Compounds

A stable and structurally well-defined titanium alkoxide catalyst supported on a metal-organic-framework (MOF) of UiO-67 topology (ANL1-Ti(OiPr)2) was synthesized and fully characterized by a variety of analytical and spectroscopic techniques, including BET, TGA, PXRD, XAS, DRIFT, SEM, and DFT computations. The Ti-functionalized MOF was demonstrated active for the catalytic hydroboration of a wide range of aldehydes and ketones with HBpin as the boron source. Compared to traditional homogeneous and supported hydroboration catalysts, ANL1-Ti(OiPr)2 is completely recyclable and reusable, making it a promising hydroboration catalyst alternative for green and sustainable chemical synthesis. In addition, ANL1-Ti(OiPr)2 catalyst exhibits remarkable hydroboration selectivity toward aldehydes vs ketone in competitive study. DFT calculations suggest that the catalytic hydroboration proceeds via a (1) hydride transfer between the active Ti-hydride species and a carbonyl moiety (rate-determining step) and (2) alkoxide transfer (intramolecular σ-bond metathesis) to generate the borate ester product.

Grignard reagents-catalyzed hydroboration of aldehydes and ketones

Simple, commercially available Grignard reagents have been used as highly efficient precatalysts for the hydroboration of a wide range of aldehydes and ketones. The reaction employs very low catalyst loadings (aldehydes: 0.05 mol%, ketones: 0.5 mol%), and

Two-coordinate terminal zinc hydride complexes: Synthesis, structure and preliminary reactivity studies

The first examples of essentially two-coordinate, monomeric zinc hydride complexes, LZnH (L = -N(Ar)(SiR3)) (Ar = C6H2{C(H)Ph2}2R′-2,6,4; R = Me, R′ = Pri (L′); R = Pri, R′ = Me

Aluminum-Hydride-Catalyzed Hydroboration of Carbon Dioxide

This study describes the first use of a bis(phosphoranyl)methanido aluminum hydride, [ClC(PPh2NMes)2AlH2] (2, Mes = Me3C6H2), for the catalytic hydroboration of CO2. Complex 2 was synthesized by the reaction of a lithium carbenoid [Li(Cl)C(PPh2NMes)2] with 2 equiv of AlH3·NEtMe2 in toluene at -78 °C. 2 (10 mol %) was able to catalyze the reduction of CO2 with HBpin in C6D6 at 110 °C for 2 days to afford a mixture of methoxyborane [MeOBpin] (3a; yield: 78%, TOF: 0.16 h-1) and bis(boryl)oxide [pinBOBpin] (3b). When more potent [BH3·SMe2] was used instead of HBpin, the catalytic reaction was extremely pure, resulting in the formation of trimethyl borate [B(OMe)3] (3e) [catalytic loading: 1 mol % (10 mol %); reaction time: 60 min (5 min); yield: 97.6% (>99%); TOF: 292.8 h-1 (356.4 h-1)] and B2O3 (3f). Mechanistic studies show that the Al-H bond in complex 2 activated CO2 to form [ClC(PPh2NMes)2Al(H){OC(O)H}] (4), which was subsequently reacted with BH3·SMe2 to form 3e and 3f, along with the regeneration of complex 2. Complex 2 also shows good catalytic activity toward the hydroboration of carbonyl, nitrile, and alkyne derivatives.

Novel aluminium compounds derived from Schiff bases: Synthesis, characterization and catalytic performance in hydroboration

Seven novel aluminium complexes supported by Schiff base ligands derived from o-diaminobenzene or o-aminothiophenol were synthesized and characterized. The reactions of AlMe3 with L1 (N,N′-bis(benzylidine)-o-phenylenediamine) and Ls

Alkaline Earth Metal Compounds of Methylpyridinato β-Diketiminate Ligands and Their Catalytic Application in Hydroboration of Aldehydes and Ketones

Ever increasing demand for green and sustainable chemical processes has set up a drive to replace transition metals with earth-abundant, nontoxic, and environmentally benign alternatives. In this regard, the alkaline earth metal complexes have attracted s

Lithium diamidodihydridoaluminates: Bimetallic cooperativity in catalytic hydroboration and metallation applications

Cooperativity between the Li and Al centres is implicated in catalytic hydroboration reactions of aldehydes and ketones with pinacolborane via heteroleptic lithium diamidodihydridoaluminates. In addition to implementing hydroalumination, these versatile heteroleptic ates can also perform as amido bases as illustrated with an acidic triazole.

Alkoxide-catalyzed reduction of ketones with pinacolborane

The reduction of ketones with pinacolborane (4,4,5,5-tetramethyl-1,3,2- dioxaborolane) is catalyzed by 5 mol % NaOt-Bu at ambient temperature. The reaction is high yielding and general, providing complete conversion of aryl and dialkyl ketones. Although spectroscopic studies of the active hydride source in benzene-d6 were complicated due to poor solubility, the data are consistent with the active hydride source being the trialkoxyborohydride, which is believed to be present in low concentration under the reaction conditions. Performing analogous studies in tetrahydrofuran resulted in a complex equilibrium between several different boron-containing species in which the trialkoxyborohydride compound was the major species.

Space Craft-like Octanuclear Co(II)-Silsesquioxane Nanocages: Synthesis, Structure, Magnetic Properties, Solution Behavior, and Catalytic Activity for Hydroboration of Ketones

Two novel space craft-like octanuclear Co(II)-silsesquioxane nanocages, {Co8[(MeSiO2)4]2(dmpz)8} (SD/Co8a) and {Co8[(PhSiO2)4]2(dmpz)8} (SD/Co8b)

Structural Elucidation of Silver(I) Amides and Their Application as Catalysts in the Hydrosilylation and Hydroboration of Carbonyls

This study details the isolation and characterisation of three novel silver(I) amides in solution and solid-state, [Ag(Cy3P)(HMDS)] 2, [Ag(Cy3P){N(TMS)(Dipp)}] 3 and [Ag(Cy3P)2(NPh2)] 4. Their catalytic abilities have proved successful in hydroboration and hydrosilylation reactions with a full investigation performed with complex 2. Both protocols proceed under mild conditions, displaying exceptional functional-group tolerance and chemoselectivity, in excellent conversions at competitive reaction times. This work reveals the first catalytic hydroboration of aldehydes and ketones performed by a silver(I) catalyst.

Synthesis, characterization, and catalytic performance of aluminum and Tin(II) compounds supported by β-diketiminato ligands

The four-coordinated bis(benzyl sulfide) complex L1Al(SCH2Ph)2 (1) was synthesized in good yield by reacting one equivalent of L1AlH2 (L1 = HC(CMeNAr)2, Ar = 2,4,6-Me3C6H2) with two equivalents of benzyl mercaptan. The reactions of L2Li (L2 = HC(CMeNAr)2, Ar = 2-iPrC6H4) with SnCl2 and AlCl3 in a molar ratio of 1:1 were carried out at room temperature, resulted in two new compounds, CH{(CH3)CN-2-iPrC6H4}2SnCl (2) and CH{(CH3)CN-2-iPrC6H4}2AlCl2 (3). All compounds were characterized by 1H NMR and 13C NMR spectroscopy, single crystal X-ray structural analysis and elemental analysis. The efficient catalytic performances of 1–3 for the hydroboration of organic compounds with carbonyl groups were investigated.

Donor-influenced Structure–Activity Correlations in Stoichiometric and Catalytic Reactions of Lithium Monoamido-Monohydrido-Dialkylaluminates

A series of heteroleptic monoamido-monohydrido-dialkylaluminate complexes of general formula [iBu2AlTMPHLi?donor] were synthesized and characterised in solution and in the solid state. Applying these complexes in catalytic hydroboration reactio

Synthesis and Structure of a Dimeric Yttrium Complex [LSi(BH3)(C5Me4)Y(CH2SiMe3)2]2(L = PhC(N tBu)2) and Its Catalytic Application for Hydroboration of Ketones and Aldehydes

Treatment of cyclopentadienyl-amidinate silylene LSi(C5HMe4) (L = PhC(NtBu)2, 1) with BH3·THF yielded the silylene-borane-functionalized tetramethylcyclopentadiene LSi(BH3)-(C5HMe4) (2), which reacted with Y(CH2SiMe3)3(THF)2 to give the dimeric yittrium complex [LSi(BH3)-(C5Me4)Y(CH2SiMe3)2]2 (3). X-ray structural analysis disclosed that the dimeric structure was formed through the BH3 bridging to the yttrium atom. Complex 3 enabled catalytic hydroboration of ketones and aldehydes with excellent efficiency and chemoselectivity.

Hidden Boron Catalysis: Nucleophile-Promoted Decomposition of HBpin

Simple nucleophiles with structural similarities to known hydroboration catalysts can readily mediate the formation of BH3 and borohydride species from pinacolborane (HBpin). Alkyne and alkene hydroboration reactions were successfully mediated by nucleophiles through BH3 generation, with BH3-catalyzed hydroboration found to dominate catalysis. NMR spectroscopy and kinetic analyses showed that the nucleophiles NaOtBu, Na[N(SiMe3)2], nBu2Mg, and nBuLi only promoted the formation of BH3 and were not "true" hydroboration catalysts.