2203-13-6

Upstream product

• 75-91-2 tert.-butylhydroperoxide 
• 122-01-0 4-chloro-benzoyl chloride 
• 10364-95-1 1-(4-chloro-benzoyl)-1H-imidazole 
• 873-76-7 para-Chlorobenzyl alcohol 
• 140-53-4 p-chlorobenzyl cyanide 
• 106-43-4 para-chlorotoluene 
• 74-11-3 para-chlorobenzoic acid 
• 104-88-1 4-chlorobenzaldehyde 

Downstream Products

• 19207-87-5 (methylthio)methyl 4-chlorobenzoate 
• 75-65-0 tert-butyl alcohol 
• 63591-89-9 1,3-dioxoisoindolin-2-yl 4-chlorobenzoate 
• 1284251-42-8 4-chlorobenzoic acid [1,4]dioxan-2-yl ester 

Relevant academic research and scientific papers

Immobilization of (l)-valine and (l)-valinol on SBA-15 nanoporous silica and their application as chiral heterogeneous ligands in the Cu-catalyzed asymmetric allylic oxidation of alkenes

SBA-15 nanoporous silica was synthesized by hydrothermal method using P123 surfactant and tetraethoxyortosilicate in acidic condition and then functionalized by 3-chloropropyltrimethoxysilane. Next, by immobilization of chiral amino acid (S)-2-amino-3-methyl butanoic acid (l-valine) and chiral amino alcohol (S)-2-amino-3-methylbutane-1-ol (l-valinol), preparedviathe reduction ofl-valine by NaBH4/I2in THF, on functionalized-SBA-15, chiral heterogeneous ligands AL*-i-Pr-SBA-15 and AA*-i-Pr-SBA-15 were prepared and characterized by FT-IR, XRD, TGA, EDX, SEM, BET-BJH techniques. The asymmetric allylic oxidation of alkenes was done using copper-complexes of these ligands and the as-synthesized peresters. The reactions were optimized by varying various parameters such as temperature, solvent, amount of chiral heterogeneous ligand, as well as the type and amount of copper salt. Under optimized conditions, 6 mg of AL*-i-Pr-SBA-15 and 3.2 mol% of Cu(CH3CN)4PF6in acetonitrile at 50 °C, the chiral allylic ester was obtained with 80% yield and 39% enantiomeric excess in 24 h. The recyclability of the chiral heterogeneous catalysts was also evaluated without significant reduction in the reaction results up to three runs.

2-Aminopyrazine-functionalized MCM-41 nanoporous silica as a new efficient heterogeneous ligand for Cu-catalyzed allylic C–H bonds oxidation of olefins

In spite of the importance of the application of allylic C–H bond oxidation of olefins in organic synthesis and existence of the numerous reports, lots of limitations such as large excess of the olefin respect to the oxidant, low chemical yield, long time of reaction and a large amount of the catalyst were reminded. We introduced a novel catalytic system using functionalized MCM-41 as catalyst support to promote efficiency of this reaction. The heterogeneous ligand Pyr-MCM-41 was prepared by substituted 2-aminopyrazine ligand on functionalized MCM-41 with 3-chloropropyltrimthoxysilane and characterized by FT-IR, XRD, SEM, EDX, BET, TGA, CHN techniques. In situ immobilized Pyr-MCM-41 by copper (I) trifluoromethanesulfonate (CuOTf) was applied in direct catalytic esterification of inert C–H bonds in olefins using various peresters at room temperature.

A Woven Supramolecular Metal-Organic Framework Comprising a Ruthenium Bis(terpyridine) Complex and Cucurbit[8]uril: Enhanced Catalytic Activity toward Alcohol Oxidation

The self-assembly of a diamondoid woven supramolecular metal–organic framework wSMOF-1 has been achieved from intertwined [Ru(tpy)2]2+ (tpy=2,2′,6′,2′′-terpyridine) complex M1 and cucurbit[8]uril (CB[8]) in water, where the intermolecular dimers formed by the appended aromatic arms of M1 are encapsulated in CB[8]. wSMOF-1 exhibits ordered pore periodicity in both water and the solid state, as confirmed by a combination of 1H NMR spectroscopy, UV-vis absorption, isothermal titration calorimetry, dynamic light scattering, small angle X-ray scattering and selected area electron diffraction experiments. The woven framework has a pore aperture of 2.1 nm, which allows for the free access of both secondary and primary alcohols and tert-butyl hydroperoxide (TBHP). Compared with the control molecule [Ru(tpy)2]Cl2, the [Ru(tpy)2]2+ unit of wSMOF-1 exhibits a remarkably higher heterogeneous catalysis activity for the oxidation of alcohols by TBHP in n-hexane. For the oxidation of 1-phenylethan-1-ol, the yield of acetophenone was increased from 10 percent to 95 percent.

Microfluidic Synthesis of tert-Butyl Peresters via KI-Catalyzed Oxidative Coupling of Methyl Arenes and tert-Butyl Hydroperoxide

A green and efficient organic-aqueous two-phase reaction route for the synthesis of tert-butyl peresters by KI-catalyzed C-H oxidation of methyl arenes in a microfluidic chip reactor has been developed. Moreover, a series of tert-butyl perester products were obtained in moderate to good yields under metal-free conditions. A scale-up continuous flow system was constructed to verify the application of this method.

Temperature-controlled solvent-free selective synthesis of tert-butyl peresters or acids from benzyl cyanides in the presence of the TBHP/Cu(OAc)2 system

Solvent-free room temperature synthesis of tert-butyl peresters was achieved via copper-catalyzed oxidative-coupling of benzyl cyanides with tert-butyl hydroperoxide in short reaction times. Various derivatives of tert-butyl peresters were synthesized by this pathway in good to excellent yields. Further investigation revealed that the above-mentioned protocol is effective for the synthesis of benzoic acid derivatives when the reaction is conducted at 80?°C, under the same reaction conditions.

Bu4NI-catalyzed construction of tert-butyl peresters from alcohols

A new method for the synthesis of tert-butyl peresters directly from available alcohols catalyzed by Bu4NI at room temperature in an aqueous system was developed. Additionally, allylic esters could also be obtained by combing this method and Kharasch-Sosnovsky reaction via a two-step one-pot procedure.

Exploring the scope of pyridyl- and picolyl-functionalized 1,2,3-triazol-5-ylidenes in bidentate coordination to ruthenium(II) cymene chloride complexes

1-(2-Pyridyl)-, 4-(2-pyridyl)-, 1-(2-picolyl)-, and 4-(2-picolyl)- functionalized 1,3,4-trisubstituted 1,2,3-triazolium salts (1A-D, respectively) were investigated as N-heterocyclic carbene (trzNHC) precursors for bidentate coordination to ruthenium(II) through the CNHC and N pyridyl donors. In addition to the pyridyl and picolyl pendant groups, a variety of para-substituted phenyl rings were attached to the 1,2,3-triazolylidene via carbon or nitrogen atoms. The ruthenation was accomplished by metalation with Ag2O to form intermediate silver carbene complexes and subsequent transmetalation with [Ru(η6-p- cymene)Cl2]2. The cationic ruthenium complexes [Ru(η6-p-cymene)(trzNHC)Cl]+ (3A-C) were readily obtained with 1-(2-pyridyl)-, 4-(2-pyridyl)-, and 1-(2-picolyl)-1,2,3-triazolium salts (1A-C) but not with the 4-picolyl analogue (1D). The bidentate coordination of the ligand precursors 1 was followed by multinuclear NMR spectroscopy, revealing significant changes in chemical shifts for triazole C-5, pyridine nitrogen atoms, and the neighboring α-proton (H-6 pyridyl) in 13C, 15N, and 1H NMR spectra. The molecular composition of complexes 3A-C was confirmed by elemental analysis and positive ion electrospray ionization (ESI+) mass spectra, the latter showing ions corresponding to [Ru(η6-p-cymene)(trzNHC)Cl] +. The solid-state structures of the three representative complexes were confirmed by single-crystal X-ray analyses; all complexes displayed a typical piano-stool type configuration. Preliminary catalytic activity screening of 3A-C in the oxidation of selected primary and secondary alcohols with tert-butyl hydroperoxide (TBHP) to give carbonyl compounds is also discussed.

Synthesis of tert-butyl peresters from aldehydes by Bu4NI- catalyzed metal-free oxidation and its combination with the Kharasch-Sosnovsky reaction

A new tert-butyl peresters synthesis directly from aldehydes and TBHP was developed via Bu4NI-catalyzed aldehyde C-H oxidation. Mechanistic studies suggest that the protocol proceeds via a radical process. Combining the method with the Kharasch-Sosnovsky reaction offers a practical approach for the synthesis of allylic esters from simple aldehydes and alkenes via a two-step one-pot procedure.

Studies on enantioselective allylic oxidation of olefins using peresters catalyzed by Cu(I)-complexes of chiral pybox ligands

Enantioselective allylic oxidation of olefins with various peresters, using a catalytic amount of Cu(i)-pybox complex, can be tuned to achieve high asymmetric induction (up to 98% ee) by choosing a unique combination of a ligand and a perester at room temperature. The asymmetric induction in the reaction strongly depends on the nature of the substituents attached to the aryl ring of peresters. The presence of a gem-diphenyl group at C-5 and secondary or tertiary alkyl substituents at the chiral center (C-4) of the oxazoline rings is crucial for high enantioselectivity. A π-π stacking model has been proposed and discussed to explain the stereochemical outcome of the reaction. The Royal Society of Chemistry 2006.

Catalytic enantioselective allylic oxidation of olefins with copper(I) catalysts and new perester oxidants

Asymmetric allylic oxidation of cyclic olefins using a catalytic amount of copper(I) bisoxazoline complexes and new peresters was investigated to give allylic benzoate esters in high selectivity (~80%ee), yield (70-80%), and at reasonable rates (5-7 d) at