107271-15-8

Upstream product

• 101286-53-7 (1RS:2SR)-2-amino-1-phenyl-1-p-tolyl-propanol-⁽¹⁾ 
• 146767-34-2 4-Methylphenylazo tert-butyl sulfide 
• 93-55-0 1-phenyl-propan-1-one 
• 140244-83-3 (Z)-(4-methylphenyl)azo tert-butyl sulfide 
• 106-43-4 para-chlorotoluene 
• 3899-96-5 4-methylphenyl tosylate 
• 106-38-7 para-bromotoluene 
• 29540-83-8 p-tolyl triflate 
• 622-97-9 1-ethenyl-4-methylbenzene 
• 93-97-0 benzoic acid anhydride 
• 1221794-80-4 tri-n-propyl[[(1Z)-1-phenyl-1-propenyl]oxy]silane 
• 65335-80-0 dimethylphenyl[[(1Z)-1-phenyl-1-propenyl]oxy]silane 
• 93-54-9 1-Phenyl-1-propanol 
• 673-32-5 1-Phenylprop-1-yne 

Downstream Products

• 107271-16-9 C₁₉H₂₄OSi 
• 107271-17-0 C₁₉H₂₄OSi 
• 1361326-28-4 2-(4-methylphenyl)-2-hydroxy-phenylpropan-1-one 
• 107271-14-7 2-Bromo-1-phenyl-2-p-tolyl-propan-1-one 
• 644995-50-6 2-phenyl-3-(4-methylphenyl)but-1-ene 

Relevant academic research and scientific papers

Progress in the Palladium-Catalyzed α-Arylation of Ketones with Chloroarenes

Non- and deactivated chloroarenes can be coupled with a wide range of ketones to yield the corresponding arylmethyl ketones in good to excellent yields using a palladium(II) acetate/n-BuPAd2 catalyst system. Depending on the ketone, the chloroarene/ketone ratio and the base, mono or diarylation can be effected selectively.

Nickel(II) complexes of highly ω'-donating cyclic (alkyl)(amino)- and malonate-carbenes: Syntheses and catalytic studies

[NiCl2(PPh3)2] reacted with the cyclic (alkyl)-(amino)carbene IPr-CAACMe2-Cy (a) and with the anionic malonate-carbene Mes-maloNHCMe-Mes (b) to give the neutral and zwitterionic complexes [NiCl2(IPr-CAACMe2-Cy)(PPh3)] (1a) and [NiCl(Mes-maloNHCMe-Mes)(PPh3)2] (3b), resulting from the respective substitution of one neutral triphenylphosphine (L-type) and one anionic chloride (X-type) ligand. Complex 1a decomposed in the presence of traces of protons to give the nickelate salt [(IPr-CAACMe2-Cy)·H][NiCl3(PPh3)] (2a). Complex 3b was insoluble in most organic solvents and thus difficult to purify and characterize, but the propensity of b to substitute X-type ligands was further illustrated by the substitution of iodide from the N-heterocyclic carbene complex [NiICp(IMe)] to give the zwitterionic heteroleptic biscarbene complex [NiCp(IMe)(Mes-maloNHCMe-Mes)] (4b), which was characterized by X-ray crystallography. The latter was postfunctionalized by the addition of methyl triflate on the malonate moiety to give the corresponding cationic species [NiCp(IMe)(Mes-maloNHCMeMe-Mes)](OTf) (5c), in which the ligand electron donicity is greatly reduced. Complexes 3b, 4b, and 5c are the first Ni(maloNHC) species, and 1a joins a very restricted list of Ni(CAAC) complexes. The catalytic activity of 1a, 4b, and 5c was studied in a cross-coupling reaction, a reduction reaction of a C-heteroatom double bond, and a C-H bond functionalization reaction.

α-arylation of ketones using highly active, air-stable (DtBPF)PdX2 (X = Cl, Br) catalysts

α-Arylation of various ketones with aryl chlorides and bromides using the well-defined and air-stable (DtBPF)PdX2 (X = Cl, Br) catalysts gave 80-100% yield of the coupled products under relatively mild conditions at low catalyst loadings. The X

Synthesis and X-ray structure determination of highly active Pd(II), Pd(I), and Pd(0) complexes of Di(tert -butyl)neopentylphosphine (DTBNpP) in the arylation of amines and ketones

The air-stable complex Pd(eta;3-allyl)(DTBNpP)Cl (DTBNpP = di(tert-butyl)neopentylphosphine) serves as a highly efficient precatalyst for the arylation of amines and enolates using aryl bromides and chlorides under mild conditions with yields ranging from 74% to 98%. Amination reactions of aryl bromides were carried out using 1-2 mol % Pd(η3-allyl)(DTBNpP)Cl at 23-50 °C without the need to exclude oxygen or moisture. The C-N coupling of the aryl chlorides occurred at relatively lower temperature (80-100 °C) and catalyst loading (1 mol %) using the Pd(eta;3-allyl) (DTBNpP)Cl precatalyst than the catalyst generated in situ from DTBNpP and Pd2(dba)3 (100-140 °C, 2-5 mol % Pd). Other Pd(DTBNpP)2-based complexes, (Pd(DTBNpP)2 and Pd(DTBNpP)2Cl2) were ineffective precatalysts under identical conditions for the amination reactions. Both Pd(DTBNpP)2 and Pd(DTBNpP)2Cl2 precatalysts gave nearly quantitative conversions to the product in the α-arylation of propiophenone with p-chlorotoluene and p-bromoanisole at a substrate/catalyst loading of 100/1. At lower substrate/ca'alyst loading (1000/1), the conversions were lower but comparable to that of Pd(t-Bu3P)2. In many cases, the tri-tert-butylphosphine (TTBP) based Pd(I) dimer, [Pd(μ-Br)(TTBP)] 2, stood out to be the most reactive catalyst under identical conditions for the enolate arylation. Interestingly, the air-stable Pd(I) dimer, Pd2(DTBNpP)2(μ-Cl)(μ-allyl), was less active in comparison to [Pd(μ-Br)(TTBP)]2 and Pd(eta;3-allyl) (DTBNpP)Cl. The X-ray crystal structures of Pd(eta;3-allyl)(DTBNpP) Cl, Pd(DTBNpP)2Cl2, Pd(DTBNpP)2, and Pd 2(DTBNpP)2(μ-Cl)(μ-allyl) are reported in this paper along with initial studies on the catalyst activation of the Pd(eta;3-allyl)(DTBNpP)Cl precatalyst.

Experimental and theoretical approaches to the influence of the addition of pyrene to a series of Pd and Ni NHC-based complexes: Catalytic consequences

A series of Ni and Pd complexes with three different N-heterocyclic carbene (NHC)-based ligands (imidazolylidene, benzimidazolylidene and pyrene-imidazolylidene) has been prepared and fully characterized. The influence of the addition of pyrene to solutions containing these complexes is studied by means of NMR and UV/Vis spectroscopies and by cyclic voltammetry. The addition of pyrene to the pyrene-NHC-containing Pd and Ni complexes gives rise to the formation of adducts by π-π stacking interactions between pyrene and the pyrene group of the NHC ligand. This interaction causes a modification of the electronic properties of the metal, as demonstrated by cyclic voltammetric studies of the Ni-NHC complexes. Theoretical calculations support this type of π-interactions, and justify the higher interactions observed with the pyrene-NHC containing complexes. The catalytic activities of the complexes were tested in the Suzuki-Miyaura C-C coupling and in the α-arylation of ketones. The addition of pyrene as an external π-stacking additive does not affect the activities of the complexes in the Suzuki-Miyaura coupling, but this observation may be justified due to the fact that the process is heterogeneously catalyzed, as indicated by the mercury-drop test. The addition of pyrene to the catalytic α-arylation of ketones results in a decrease in the activity of the reactions catalyzed by the pyrene-imidazolylidene palladium complex, whereas the other two catalysts do not modify their activity in the presence of this π-stacking additive.

Synthesis of novel (NHC)Pd(acac)Cl complexes (acac=acetylacetonate) and their activity in cross-coupling reactions

The synthesis and characterization of two new complexes (IPr)Pd(acac) 2 (1) and (IPr)Pd(acac)Cl (2) (IPr=(N,N′-bis(2,6- diisopropylphenyl)imidazol)-2-ylidene, acac=acetylacetonate) are described. Complex 2 can be prepared in a one-pot protocol in high yield. A study detailing the versatility of 2 to effectively catalyze a series of cross-coupling reactions is discussed.

Simple, highly active palladium catalysts for ketone and malonate arylation: Dissecting the importance of chelation and steric hindrance

A remarkably active catalyst system for α-arylation of ketones and malonates was developed by proposing that sterically hindered alkylphosphines would accelerate the catalytic reaction rates. We initially tested the bisphosphine ligand D'BPF (1,1'-bis-(di-tert-butylphosphino)ferrocene) for this palladium-catalyzed chemistry. This catalyst system led to fast reaction rates for reactions of aryl bromides with ketones, including room temperature chemistry in many cases. In some cases turnover numbers were 20 000. The catalyst also gave mild reactions with aryl chlorides with yields that were similar to the chemistry with aryl bromides. Independent synthesis of the arylpalladium enolate complexes with isobutyrophenone enolate showed that only one phosphorus of the bisphosphine ligand D'BPF was coordinated in the enolate complex. Thus, we tested sterically hindered alkylphosphine ligands for the ketone and malonate arylation process and found that P(t-Bu)3 gave exceptionally fast rates and high turnover numbers for these reactions. These results demonstrate several principles for the catalytic chemistry that we did not anticipate: palladium complexes of monophosphine ligands can activate aryl chlorides under mild conditions, and palladium enolates coordinated by certain monophosphines can undergo C-C bond-forming reductive elimination much faster than β-hydrogen elimination.

Highly active and selective catalysts for the formation of α-aryl ketones

Bulky, electron-rich phosphine ligands with a biphenyl backbone, when combined with Pd(OAc)2, give highly active catalysts for the α-arylation of ketones. The ligand 2-methyl-2'-dicyclohexylphosphinobiphenyl is particularly effective, and with

Structural, Computational, and Spectroscopic Investigation of [Pd(κ3-1,1′-bis(di-tert-butylphosphino)ferrocenediyl)X]+ (X = Cl, Br, I) Compounds

The reaction of [Pd(dtbpf)Cl2] (dtbpf = 1,1′-bis(di-tert-butylphosphino)ferrocene) with sodium bromide yields [Pd(dtbpf)Br][Br], which displays an interaction between the iron and palladium atoms. The structure of this compound has been obtained and is compared to those of the previously reported [Pd(dtbpf)X]+ (X = Cl, I) analogues. Similar to [Pd(dtbpf)Cl]+, [Pd(dtbpf)Br]+ appears to undergo a solid-state isomerization at low temperature to a species in which the Fe-Pd interaction is disrupted. In addition to 1H and 31P{1H} NMR and visible spectroscopy, the [Pd(dtbpf)X]+ (X = Cl, Br) compounds were also characterized by zero-field 57Fe M?ssbauer spectroscopy. DFT calculations on [Pd(dtbpf)X]+ (X = Cl, Br, I) show that the Fe-Pd interaction is weak and noncovalent and that the strength of the interaction decreases as the halide becomes larger. A related trend is noted in the potential at which oxidation of the iron center occurs; the larger the halide, the less positive the potential at which oxidation occurs. Finally, the catalytic activity of [Pd(dtbpf)X]+ (X = Cl, Br, I) in the arylation of an aromatic ketone was examined and compared to the activity of [Pd(dtbpf)Cl2].

N-heterocyclic carbene-palladium complexes [(NHC)Pd(acac)Cl]: Improved synthesis and catalytic activity in large-scale cross-coupling reactions

From two commercially available starting materials, improved one-step, multigram-scale syntheses of [(IPr)Pd(acac)Cl] [IPr = N,N′-bis(2,6- diisopropylphenyl)imidazol-2-ylidene ; acac = acetylacetonate] and [(IMes)Pd(acac)Cl] [IMes=N,N′-bis(2,4,6-trimethyl