85609-08-1

Upstream product

• 74231-65-5 p-cyano-1-(dichloromethyl)benzene 
• 71-43-2 benzene 
• 57808-43-2 4-(hydroxy(diphenyl)methyl)benzonitrile 
• 5410-05-9 ((4-bromophenyl)methylene)dibenzene 
• 7758-99-8 copper(II) sulfate 
• 104-85-8 para-methylbenzonitrile 
• 101-81-5 Diphenylmethane 
• 623-00-7 4-bromobenzenecarbonitrile 
• 126747-14-6 4-cyanophenylboronic acid 
• 91-01-0 1,1-Diphenylmethanol 
• 1194-02-1 4-fluorobenzonitrile 
• 623-03-0 4-Cyanochlorobenzene 
• 105-07-7 4-cyanobenzaldehyde 

Downstream Products

• 6328-81-0 4-benzhydrylbenzoic acid 

Relevant academic research and scientific papers

Synthesis of Triarylmethanes via Palladium-Catalyzed Suzuki-Miyaura Reactions of Diarylmethyl Esters

The synthesis of triarylmethanes via Pd-catalyzed Suzuki-Miyaura reactions between diarylmethyl 2,3,4,5,6-pentafluorobenzoates and aryl boronic acids is described. The system operates under mild conditions and has a broad substrate scope, including the coupling of diphenylmethanol derivatives that do not contain extended aromatic substituents. This is significant as these substrates, which result in the types of triarylmethane products that are prevalent in pharmaceuticals, have not previously been compatible with systems for diarylmethyl ester coupling. Furthermore, the reaction can be performed stereospecifically to generate stereoinverted products. On the basis of DFT calculations, it is proposed that the oxidative addition of the diarylmethyl 2,3,4,5,6-pentafluorobenzoate substrate occurs via an SN2 pathway, which results in the inverted products. Mechanistic studies indicate that oxidative addition of the diarylmethyl 2,3,4,5,6-pentafluorobenzoate substrates to (IPr)Pd(0) results in the selective cleavage of the O-C(benzyl) bond in part because of a stabilizing η3-interaction between the benzyl ligand and Pd. This is in contrast to previously described Pd-catalyzed Suzuki-Miyaura reactions involving phenyl esters, which involve selective cleavage of the C(acyl)-O bond, because there is no stabilizing η3-interaction. It is anticipated that this fundamental knowledge will aid the development of new catalytic systems, which use esters as electrophiles in cross-coupling reactions.

Synthesis of Triarylmethanes via Palladium-Catalyzed Suzuki Coupling of Trimethylammonium Salts and Arylboronic Acids

An efficient palladium-catalyzed Suzuki coupling of 1,1-diarylmethyl-trimethylammonium triflates with arylboronic acids is reported. This reaction offers a novel approach to triarylmethane derivatives in good to excellent yields with the palladium-catalyzed C-N bond cleavage as the key feature. Broad substrate scope regarding both reaction partners are observed. Moreover, reactive functional groups such as vinyl and formyl groups are conserved in this transformation.

LDA-Mediated Synthesis of Triarylmethanes by Arylation of Diarylmethanes with Fluoroarenes at Room Temperature

A practical and convenient approach for the secondary C(sp3)-H arylation of diarylmethanes with various fluoroarenes is described. The reaction proceeds smoothly in the presence of LDA (lithium diisopropylamide) at room temperature and affords triarylmethanes in moderate to high yields.

NiXantphos: A deprotonatable ligand for room-temperature palladium-catalyzed cross-couplings of aryl chlorides

Although the past 15 years have witnessed the development of sterically bulky and electron-rich alkylphosphine ligands for palladium-catalyzed cross-couplings with aryl chlorides, examples of palladium catalysts based on either triarylphosphine or bidentate phosphine ligands for efficient room temperature cross-coupling reactions with unactivated aryl chlorides are rare. Herein we report a palladium catalyst based on NiXantphos, a deprotonatable chelating aryldiphosphine ligand, to oxidatively add unactivated aryl chlorides at room temperature. Surprisingly, comparison of an extensive array of ligands revealed that under the basic reaction conditions the resultant heterobimetallic Pd-NiXantphos catalyst system outperformed all the other mono- and bidentate ligands in a deprotonative cross-coupling process (DCCP) with aryl chlorides. The DCCP with aryl chlorides affords a variety of triarylmethane products, a class of compounds with various applications and interesting biological activity. Additionally, the DCCP exhibits remarkable chemoselectivity in the presence of aryl chloride substrates bearing heteroaryl groups and sensitive functional groups that are known to undergo 1,2-addition, aldol reaction, and O-, N-, enolate-α-, and C(sp2)-H arylations. The advantages and importance of the Pd-NiXantphos catalyst system outlined herein make it a valuable contribution for applications in Pd-catalyzed arylation reactions with aryl chlorides.

Additive effects on palladium-catalyzed deprotonative-cross-coupling processes (DCCP) of sp3 C-H bonds in diarylmethanes

Palladium-catalyzed cross-coupling reactions have become one of the most useful tools in modern organic chemistry. Current methods to achieve direct functionalization of sp3 C-H bonds of arenes and heteroarenes often employ substrates with appropriately placed directing groups to enable reactivity. Examples of intermolecular arylation methods of weakly acidic sp3 C-H bonds in the absence of directing groups, however, are still limited. We describe herein a study on the use of additives in Pd-catalyzed deprotonative-cross-coupling processes (DCCP) of sp3 C-H bonds of diarylmethanes with aryl bromides at room temperature. These studies resulted in development of four new efficient Pd-catalyzed DCCP using additives that enabled the generation of a range of sterically and electronically diverse aryl- and heteroaryl containing triarylmethanes in good to excellent yields. Additive identification and optimization of all reaction conditions (additive loading, solvent and temperature) were performed using high-throughput experimentation (HTE). The approach outlined herein is expected to be generalizable to other C-H functionalization reactions involving the deprotonation of weakly acidic C-H bonds. The Royal Society of Chemistry 2013.

Microwave-assisted nafion-H catalyzed friedel-crafts type reaction of aromatic aldehydes with arenes: Synthesis of triarylmethanes

A new solid acid Nafion-H, a perfluorinated sulfonic acid resin, catalyzed microwave-assisted synthesis of triarylmethanes is described. Various benzaldehydes react readily with arenes to provide the corresponding triarylmethanes in good to excellent yields. The reactions were carried out under solvent free conditions under microwave irradiation in a pressure vessel. The solvent free microwave irradiation methods appears to be an environmentally friendly synthetic protocol providing products in significantly shorter reaction times over traditional heating methods carried out in a pressure tube.

BF3-H2O catalyzed hydroxyalkylation of aromatics with aromatic aldehydes and dicarboxaldehydes: Efficient synthesis of triarylmethanes, diarylmethylbenzaldehydes, and anthracene derivatives

(Figure Presented) BF3-monohydrate is found to be an efficient and strong acid catalyst as well as an effective protosolvating medium suitable for the hydroxyalkylation of arenes with aromatic aldehydes. This reaction has been extended to aromatic dialdehydes, such as terephthalic dicarboxaldehyde and isoterephthalic dicarboxaldehyde, for the efficient synthesis of diarylmethylbenzaldehydes, which are useful synthons for various organic transformations. Further, successful one step convergent synthesis of various synthetically useful anthracene derivatives from phthalaldehyde was also achieved. BF3-H2O is less expensive and acts as an efficient substitute for nonoxidizing strong protic acids/superacids.

6-HETEROCYCLIC-4-AMINO-1,3,4,5-TETRAHYDROBENZ[CD]INDOLES

6-heterocyclic-4-amino-1,3,4,5-tetrahydrobenz[cd]indoles are provided which are useful in modifying the function of serotonin in mammals.

6-HETEROCYCLIC-4-AMINO-1,2,2A,3,4,5-HEXAHYDROBENZ[CD]INDOLES

6-Heterocyclic-4-amino-l,2,2a,3,4,5-hexahydrobenz[cd]indoles are provided which are useful in modifying the function of serotonin in mammals.

6-heterocyclic-4-amino-1,2,2a,3,4,5-hexahydrobenz(cd)indoles and pharmaceutical use thereof

6-Heterocyclic-4-amino-1,2,2a,3,4,5-hexahydrobenz[cd]indoles are provided which are useful in modifying the function of serotonin in mammals.