21846-08-2

Upstream product

• 1689-64-1 9-Fluorenol 
• 100-66-3 methoxybenzene 
• 12257-35-1 9-fluorenyl carbocation 
• 1065544-00-4 (biphenyl-2-yl)(4-methoxyphenyl)methanol 
• 1065544-24-2 acetic acid (biphenyl-2-yl)(4-methoxyphenyl)methyl ester 
• 86-73-7 9H-fluorene 
• 623-12-1 4-chloromethoxybenzene 
• 123-11-5 4-methoxy-benzaldehyde 
• 14202-31-4 4-methoxybenzaldehyde-1,1-diacetate 
• 486-25-9 9-fluorenone 
• 5720-07-0 4-methoxyphenylboronic acid 
• 1016-05-3 dibenzothiophene sulfone 
• 104-47-2 p-methoxybenzylnitrile 
• 459-60-9 1-fluoro-4-methoxybenzene 

Relevant academic research and scientific papers

Transition-Metal-Free Synthesis of Polyfunctional Triarylmethanes and 1,1-Diarylalkanes by Sequential Cross-Coupling of Benzal Diacetates with Organozinc Reagents

A variety of functionalized triarylmethane and 1,1-diarylalkane derivatives were prepared via a transition-metal-free, one-pot and two-step procedure, involving the reaction of various benzal diacetates with organozinc reagents. A sequential cross-coupling is enabled by changing the solvent from THF to toluene, and a two-step SN1-type mechanism was proposed and evidenced by experimental studies. The synthetic utility of the method is further demonstrated by the synthesis of several biologically relevant molecules, such as an anti-tuberculosis agent, an anti-breast cancer agent, a precursor of a sphingosine-1-phosphate (S1P) receptor modulator, and a FLAP inhibitor.

Experimental Evidence for p Ka-Driven Asynchronicity in C-H Activation by a Terminal Co(III)-Oxo Complex

C-H activation by transition metal oxo complexes is a fundamental reaction in oxidative chemistry carried out by both biological and synthetic systems. This centrality has motivated efforts to understand the patterns and mechanisms of such reactivity. We have therefore thoroughly examined the C-H activation reactivity of the recently synthesized and characterized late transition metal oxo complex PhB (tBuIm)3CoIIIO. Precise values for the pKa and BDFEO-H of the conjugates of this complex have been experimentally determined and provide insight into the observed reactivity. The activation parameters for the reaction between this complex and 9,10-dihydroanthracene have also been measured and compared to previous literature examples. Evaluation of the rates of reaction of PhB(tBuIm)3CoIIIO with a variety of hydrogen atom donors demonstrates that the reactivity of this complex is dependent on the pKa of the substrate of interest rather than the BDEC-H. This observation runs counter to the commonly cited reactivity paradigm for many other transition metal oxo complexes. Experimental and computational analysis of C-H activation reactions by PhB(tBuIm)3CoIIIO reveals that the transition state for these processes contains significant proton transfer character. Nevertheless, additional experiments strongly suggest that the reaction does not occur via a stepwise process, leading to the conclusion that C-H activation by this CoIII-oxo complex proceeds by a pKa-driven "asynchronous" concerted mechanism. This result supports a new pattern of reactivity that may be applicable to other systems and could result in alternative selectivity for C-H activation reactions mediated by transition metal oxo complexes.

Nickel-Catalyzed C(sp3)-H Arylation of Diarylmethane Derivatives with Aryl Fluorides

A novel nickel-catalyzed C(sp3)-H arylation with nonactivated aryl fluorides is reported. The use of 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene (IMes) as a ligand was found to be critical to the success of the reaction. This new method enables the synthesis of a wide range of triarylmethane derivatives.

KHMDS mediated synthesis of 9-arylfluorenes from dibenzothiophene dioxides and arylacetonitriles by tandem SNAr-decyanation-based arylation

A straightforward KHMDS mediated synthetic route to 9-arylfluorenes from readily available starting materials has been developed. This reaction involves SNAr reactions of dioxide with arylacetonitriles, followed by decyanation reaction. The pro

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.

Solvent control of product diversity in palladium-catalyzed addition of arylboronic acid to aryl aldehydes

In Pd-catalyzed arylboronic acid addition to aryl aldehydes, the expected carbinol or asymmetrical ether can be obtained as the major product by altering aqueous solvent composition. Exploiting this methodology with 2-formylbiphenyls as reaction partner, a fluorene scaffold can be readily constructed in two steps.

Direct C-H bond arylation of fluorenes with aryl chlorides catalyzed by N-heterocyclic carbene-palladium(ii)-1-methylimidazole complex and further transformation of the products in a one-pot procedure

We report here the NHC-Pd(ii)-Im complex 1-catalyzed direct C-H bond functionalization of the C9 position of fluorenes with aryl chlorides and further transformation of the resulting products in a one-pot procedure. Under the optimal conditions, arylated fluorenes can be obtained in moderate to almost quantitative yields using various activated and unactivated (hetero)aryl chlorides as the arylating reagents. Furthermore, if the mixture from the arylation reaction is exposed to air, the C9-oxidized products can be obtained in acceptable to good yields in a one-pot procedure. In addition, alkyl groups can also be efficiently introduced to the above mixture from the arylation reaction, producing further C9-alkylated products in good to almost quantitative yields in a one-pot procedure, thus providing an expedient, inexpensive and practical strategy for the mono- and di-functionalization of fluorenes. This journal is

Iron-catalyzed arylation of aromatic ketones and aldehydes mediated by organosilanes

A simple and efficient iron-catalyzed method for arylation of aromatic carbonyl compounds is reported. The use of 4-% FeCl3 or Fe(acac) 3 as the catalyst, in combination with a slight excess of chlorotrimethylsilane and triethylsilane, chlorination of benzylic ketones and aldehydes with subsequent Friedel-Crafts alkylation of arenes is achieved. Although the method is limited by the general constraints associated with Friedel-Crafts alkylation reactions, robust applications for the synthesis of pharmaceutical intermediates and so on can be envisioned. A robust one-pot, iron-catalyzed chlorination Friedel-Crafts alkylation reaction of benzylic carbonyl compounds, mediated by chlorotrimethylsilane and triethylsilane, has been developed to yield substituted diaryl and triaryl building blocks. Copyright

Highly efficient synthesis of polysubstituted fluorene via iron-catalyzed intramolecular Friedel-Crafts alkylation of biaryl alcohols

An efficient and mild Fe(III)-catalyzed intramolecular Friedel-Crafts alkylation of biaryl methanol derivatives has been developed to achieve the substituted fluorene derivatives. The present reaction provides an excellent alternative to published methods

Heterobimetallic Pd-Sn catalysis: A Suzuki, tandem ring-closing sequence toward indeno[2,1-b]thiophenes and indeno[2,1-b]indoles

Indeno[2,1-b]thiophene and indeno[1,2-b]indole motifs have been obtained in moderate to good yields from easily available substituted boronic acids, 2-bromo aryl/vinyl aldehydes, and nucleophiles such as arenes/heteroarenes and others using a catalytic co