23674-13-7

Upstream product

• 90-44-8 anthracen-9(10H)-one 
• 108-88-3 toluene 
• 642-31-9 9-anthracene aldehyde 
• 1564-64-3 9-Bromoanthracene 
• 95-49-8 2-methylchlorobenzene 
• 716-53-0 9-chloroanthracene 
• 16419-60-6 2-Methylphenylboronic acid 
• 95-46-5 2-methylphenyl bromide 
• 709022-63-9 2-anthracen-9-yl-4,4,5,5-tetramethyl-[1,3,2]dioxaborolane 
• 151256-87-0 9-anthrylzinc chloride 
• 102477-77-0 2'-Methyl-2-benzyl-benzophenon 
• 932-31-0 ortho-tolylmagnesium bromide 
• 523-27-3 9,10-Dibromoanthracene 

Downstream Products

• 56985-55-8 C₂₇H₁₆F₄ 
• 56985-54-7 C₂₇H₂₀ 
• 1041847-30-6 C₂₁H₁₅Br 
• 1158844-33-7 C₆₃H₄₆ 
• 1158844-38-2 C₆₉H₅₀ 
• 23673-90-7 9-Chlor-10-(o-tolyl)-anthracen 
• 56985-56-9 C₂₇H₁₆Cl₄ 

Relevant academic research and scientific papers

Evaluation of the Transferability of the “Flexible Steric Bulk” Concept from N-Heterocyclic Carbenes to Planar-Chiral Phosphinoferrocenes and their Electronic Modification

The concept of “flexible steric bulk” is discussed at 2-phenylvinyl-1-phosphinoferrocenes. The introduction of freely rotatable 1'-silyl groups increases the catalytic productivity within the synthesis of tri-ortho-substituted biaryls by Suzuki–Miyaura C,C cross-coupling reactions, giving higher yields with 1/4 of catalyst concentration than for the non-silylated derivatives. Electronic modification of the P and the vinyl donor functionalities was investigated by introducing substituents in the para positions of both groups. Therein, electron-withdrawing phosphines increased the yield from 78 to 91 percent for a given biaryl, by changing from a diphenylphosphino to the P(p-CN-C6H4)2 unit. Opposite results, obtained from electron-donating and sterically demanding phosphines, were in accordance with the 1J(31P,77Se) values. However, the electron density of the ferrocenyl backbone, expressed by the redox potential of the first ferrocenyl-related redox process, cannot be correlated with the donor-properties at the P atom. Changing from a PPh2-substituted ferrocene to a (RA)-1,1'-binaphthyl-containing phosphonite, a complex interaction between the axial- and the planar-chiral motifs occurs, resulting a change of the absolute biaryl configuration.

Chromium- and Cobalt-Catalyzed, Regiocontrolled Hydrogenation of Polycyclic Aromatic Hydrocarbons: A Combined Experimental and Theoretical Study

Polycyclic aromatic hydrocarbons are difficult substrates for hydrogenation because of the thermodynamic stability caused by aromaticity. We report here the first chromium- and cobalt-catalyzed, regiocontrolled hydrogenation of polycyclic aromatic hydrocarbons at ambient temperature. These reactions were promoted by low-cost chromium or cobalt salts combined with diimino/carbene ligand and methylmagnesium bromide and are characterized by high regioselectivity and expanded substrate scope that includes tetracene, tetraphene, pentacene, and perylene, which have rarely been reduced. The approach provides a cost-effective catalytic protocol for hydrogenation, is scalable, and can be utilized in the synthesis of tetrabromo- and carboxyl-substituted motifs through functionalization of the hydrogenation product. The systematic theoretical mechanistic modelings suggest that low-valent Cr and Co monohydride species, most likely from zerovalent transition metals, are capable of mediating these hydrogenations of fused PAHs.

SYNTHESIS OF PHOSPHINE LIGANDS BEARING TUNABLE LINKAGE: METHODS OF THEIR USE IN CATALYSIS

A series of novel linked indolyl phosphine ligands for transition metals, the synthesis thereof and their use in catalytic coupling reactions are provided. The ligands provide improvements of trasition-metal-catalyzed reactions, including the range of substrates scope, reaction conditions and efficieny.

(Planar-Chiral) Ferrocenylmethanols: From Anionic Homo Phospho-Fries Rearrangements to α-Ferrocenyl Carbenium Ions

The reaction of FcCH2OH with chlorophosphates gave ferrocenyl phosphates FcCH2OP(O)(OR)2 [Fc = Fe(η5-C5H5)(η4-C5H4)], which readily separate into phosphate anions and ferrocenyl carbo-cations. The latter species undergoes consecutive reactions, for example, electrophilic aromatic substitutions. When nitriles, instead of alcohols, are treated with FcLi or tBuLi and chlorophosphates, chiral-pool based ferrocenylimino phosphoramidates Fc-CR=N-P(O)(OR*)2 are formed, which are promising candidates for anionic homo phospho-Fries rearrangements. Moreover, the sterically demanding chiral chlorophosphate with R* enabled oxidative couplings of the imines to form a diferrocenylazine. Similarly, the reaction of Fc–Li with 9-anthrylnitrile produced a 10-ferrocenyl-substituted product, contrary to a reaction at the C≡N functionality. A planar-chiral ortho-P(S)Ph2-functionalized ferrocenylmethanol also gave carbo-cations under acidic conditions. These species can be sulfurized in a unique way giving thio ethers, whereby the in situ formed 1,2-P(S)Ph2,CH2+ ferrocene cation acts as the sulfur and electron source. However, lowering the substrate concentration prevents sulfur migration, resulting in electrophilic substitution reactions with aromatic solvents. Planar-chiral ferrocenylmethyl thio or anisyl derivatives were applied as ligands in Pd-catalyzed Suzuki–Miyaura C,C cross-couplings for the atroposelective synthesis of hindered biaryls with up to 26 % ee at low catalyst loadings (1 mol-% Pd).

Resorcinarene-Based o-Biarylphosphines in Palladium-Catalysed Suzuki–Miyaura Cross-Coupling Reactions of Bulky Substrates

Two o-biarylphosphines, in which the arene ring remote from the phosphorus atom is part of a resorcin[4]arene cavitand, have been synthesised, characterised by X-ray diffraction and assessed in the cross-coupling reactions of bulky aryl chlorides with sterically hindered arylboronic acids. Only atropisomers with externally located P atoms were obtained. The resorcinarene ligand with the o-PCy2C6H4substituent was found to be more efficient than the Buchwald analogue SPhos in catalysing coupling reactions, reacting around 1.4 times faster. Its superior performance has been attributed to the permanent exo positioning of the metal centre, which engenders steric interactions with two pentyl substituents and therefore facilitates the reductive elimination step.

An efficient indenyl-derived phosphine ligand for the Suzuki-Miyaura coupling of sterically hindered aryl halides

An air-stable aryl substituted indenyl phosphine used in combination with Pd(OAc)2 provides a highly efficient catalyst for the Suzuki-Miyaura cross-coupling reaction of sterically hindered aryl halides with aryl boronic acids.

The Influence of Imidazolylidene Ligands with Bulky Resorcinarenyl Substituents on Catalysts for Suzuki-Miyaura Coupling

PEPPSI-type imidazolylidene palladium complexes having their carbenic ring N-substituted with an aryl ring and a cavity-shaped unit [25,26,27,28-tetrapropyloxycalix[4]aren-5-yl or 6(10),12(16),18(22)-tetramethylenedioxy-2,8,14,20-tetrapentylresorcin[4]aren-5-yl (TPR)] have been prepared and assessed in Suzuki-Miyaura cross-couplings. Remarkable efficiency in the coupling of aryl chlorides with sterically hindered arylboronic acids was observed for the carbene ligand having its N atoms (N1, N2) substituted by a mesityl and a TPR group, respectively. This good performance possibly arises from strong steric interactions between the pentyl-substituted cavitand unit and the catalytic centre, which favours reductive elimination. Two of the imidazolium salts used for complex synthesis were characterised by X-ray diffraction analysis.

Arylcalixarenyl Phosphines in Palladium-Catalyzed Suzuki-Miyaura Cross-Coupling Reactions

Two electron-rich arylcalixarenylphosphines have been synthesized in three steps from the appropriate 5-bromocalix[4]arene precursor 1. The combination of 5-(2-diisopropylphosphinophenyl)-25,26,27,28-tetrapropyloxycalix[4]arene (5) and 5-(2-dicyclohexylphosphinophenyl)-25,26,27,28-tetrapropyloxycalix[4]arene (6), respectively, with [Pd2(dba)3] (dba = dibenzylideneacetone) generated effective catalysts for the cross-coupling reactions of hindered aryl chlorides and arylboronic acids. Dicyclohexylphosphino-substituted ligand 6 had a higher activity that that of 5, and the structures of ligand 5 and [AuCl·5] were determined by single-crystal X-ray diffraction studies. The solid-state structure of [AuCl·5] revealed that the gold atom lies above the outer face of the calixarene unit, with distances of 3.08 and 3.28 ? between the gold atom and the two closest aromatic carbon atoms of the calixarene moiety.

A Planar-Chiral Phosphino(alkenyl)ferrocene for Suzuki-Miyaura C-C Coupling Reactions

Planar-chiral phosphinoferrocene [Fe(η5-C5H3-1-PPh2-2-(E)-CH=CHPh)(η5-C5H5)] (4) was applied in the presence of palladium in Suzuki-Miyaura couplings for the synthesis of sterically congested biaryls. The catalytic activity arises from homogeneous palladium phosphine complexes, of which the potential pre-catalyst [Pd(4)2Cl2] was characterized structurally. The catalytic system is excellently suited for the synthesis of tri-ortho-substituted biaryls under mild conditions (0.1 mol-%, 50-100 C), whereas its application towards the synthesis of tetra-ortho-substituted biaryls is quite limited. Comparing the performance of the reaction with 4 as catalyst and a range of substrates with differing ortho substituents suggests that transmetalation is rate determining. Complex (Sp)-4 was used in atropselective couplings, wherein enantioenrichments of up to 36 % were achieved. The stereoselectivity depends to some extent on the steric properties of the boronic acids; however, slight changes at the aryl halides influence the enantioselectivity.

Suzuki-Miyaura cross-coupling of bulky anthracenyl carboxylates by using pincer nickel N-heterocyclic carbene complexes: An efficient protocol to access fluorescent anthracene derivatives

A series of fluorescent (hetero)-aryl substituted anthracene derivatives were readily accessible from the corresponding bulky anthracen-9-yl carboxylates via Suzuki-Miyaura cross-coupling reactions by using pincer nickel N-heterocyclic carbene complex 1 even at the catalyst loading as low as 0.1 mol% in the presence of catalytic amounts of PCy3.