1143018-72-7

Upstream product

• 98-86-2 acetophenone 
• 25015-63-8 4,4,5,5-tetramethyl-[1,3,2]-dioxaboralane 
• 100-52-7 benzaldehyde 
• 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 academic research and scientific papers

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.

Coordination Chemistry of the PdmBOX Pincer Ligand: Reactivity at the Metal and the Ligand

The coordination chemistry of PdmBOX [2,5-bis(2-oxazolinyldimethylmethyl)pyrrole] pincer ligands, in which a dimethylmethylidene linker has been introduced to preclude rearrangements in the backbone, has been studied with 3d and 4d late transition metals. The in situ lithiated PdmBOX ligand was treated with MnCl2, FeCl2 and CoCl2 to give [iPr(PdmBOX)MCl] (M = Mn: 2; Fe: 3; Co: 4) which were found to adopt a distorted tetrahedral coordination geometry in the crystal. Addition of 2,6-dimethylphenylisocyanide to 3 gave the diamagnetic tris(isocyanide) derivative [iPr(PdmBOX)Fe(CNxyl)3]Cl (5) with the chloride as the counteranion. Complexes 2–4 were found to be precatalysts for the enantioselective hydrosilylation and hydroboration of acetophenone. The synthesis of PdmBOX-palladium(II) complexes was achieved by deprotonation of the protioligand with potassium bis(trimethylsilyl)amide (KHMDS) and subsequent reaction with [(cod)PdCl2] giving [iPr(PdmBOX)PdCl] (6) or by stirring (S)-iPr(PdmBOX)H with palladium acetate yielding the palladium acetato complex 7. Treatment of the latter with phenylsilane at 60 °C also led to the slow formation of the metal hydride complex which was the key species in the catalytic hydrosilylation of styrene oxide, albeit with low activity. The coordination of (S)-iPr(PdmBOX)H to rhodium(I) was accomplished by reaction with (acetylacetonato)dicarbonylrhodium(I) to give the corresponding PdmBOX-Rh complex 8 which reacted with methyl iodide to give the octahedrally coordinated rhodium(III) complex [iPr(PdmBOX)Rh(CH3)I(CO)] 9. Reaction of 8 with one equivalent of CsBr3 led to the full conversion to the dibromorhodium(III) complex [iPr(PdmBOX)Rh(CO)Br2] 10. Upon reaction of 10 with N-bromosuccinimide (NBS), the pyrrole backbone in 10 was brominated to give complex 11. In a similar way, a selective conversion of [iPr(PdmBOX)NiCl] to the backbone-chlorinated [iPr(ClPdmBOX)NiCl] (12) was achieved by the treatment with N-chlorosuccinimide.

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–

Rhenium-catalysed hydroboration of aldehydes and aldimines

The first examples for the rhenium-catalysed hydroboration of aldehydes, ketones and aldimines, including heteroaromatic quinoline, are reported herein. Reactions are remarkably chemoselective and tolerant of several functional groups. A wide array of rhenium complexes were efficient pre-catalysts for these hydroborations, including new low-valent complexes of the formula [Re(N-N)(CO)3(L)]X (N-N = bipy derivative, L = labile ligand/solvent, and X = [BArF4]- and [B(3,5-di-tBu-cat)2]-), which have been characterized fully including an X-ray diffraction study for [Re(bipy)(CO)3(quin)][BArF4] (2). A new silver spiroboronate ester Ag[B(3,5-di-tBu-cat)2](NCCH3)3 (3) was prepared and characterized fully, including an X-ray diffraction study, and used to make one of the new rhenium complexes.

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

Silyl Anion Initiated Hydroboration of Aldehydes and Ketones

Hydroboration is an emerging method for mild and selective reduction of carbonyl compounds. Typically, transition-metal or reactive main-group hydride catalysts are used in conjunction with a mild reductant such as pinacolborane. The reactivity of the main-group catalysts is a consequence of the nucleophilicity of their hydride ligands. Silicon hydrides are significantly less reactive and are therefore not efficient hydroboration catalysts. Here, a readily prepared silyl anion is reported to be an effective initiator for the reduction of aldehydes and ketones requiring mild conditions, low catalyst loadings and with a good substrate scope. The silyl anion it is shown to activate HBpin to generate a reactive borohydride in situ which reacts with aldehydes and ketones to afford the hydroboration product.

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.

Diverse Activation Modes in the Hydroboration of Aldehydes and Ketones with Germanium, Tin, and Lead Lewis Pairs

Intramolecular germylene, stannylene, and plumbylene Lewis pairs were reacted with hexanal and yielded the cyclic addition products only with the germanium and tin reagents. In further reactivity studies, the hydroboration of aldehydes and ketones catalyzed by intramolecular germylene, stannylene, and plumbylene Lewis pairs was studied. In the case of the cyclic germylene Lewis pair, the product of the oxidative addition of pinacolborane at the germylene moiety was observed. According to stoichiometric as well as catalytic experiments, the intramolecular germylene Lewis pair acts as a catalyst in the hydroboration of aldehydes and ketones. The homologous stannylene Lewis pair forms a reactive tin hydride during the catalysis, which can also act as a catalyst in this transformation.

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

Synthesis of a Base-Stabilized Silicon(I)-Iron(II) Complex for Hydroboration of Carbonyl Compounds

The reaction of the amidinatosilicon(I) dimer [LSi:]2 (1; L = PhC(NtBu)2) with FeBr2 in tetrahydrofuran (THF) at ambient temperature afforded the silicon(I)-iron(II) dimer [LSi(FeBr2·THF)]2 (2) after