350-42-5

Upstream product

• 589-18-4 4-Methylbenzyl alcohol 
• 104-87-0 4-methyl-benzaldehyde 
• 874-60-2 4-methyl-benzoyl chloride 
• 99-94-5 p-Toluic acid 
• 53358-36-4 trimethylsilyl p-methylbenzoate 
• 106-38-7 para-bromotoluene 
• 50978-45-5 3-oxobenzo[d]isothiazole-2(3H)-carbaldehyde 1,1-dioxide 
• 17264-54-9 sodium p-methylbenzoate 
• 98-88-4 benzoyl chloride 
• 120608-85-7 4-Methyl-benzoic acid difluoromethyl ester 
• 201230-82-2 carbon monoxide 

Downstream Products

• 78102-82-6 p-Toluylsaeure-fluorsulfonsaeureanhydrid 
• 99-94-5 p-Toluic acid 
• 39248-95-8 S-(p-tolyl) p-methylbenzothioathe 
• 1251445-54-1 diethyl(4-methylbenzoyl)phosphine sulfide 
• 5436-83-9 N-benzyl-4-methylbenzamide 
• 134-84-9 4-Methylbenzophenone 
• 104-87-0 4-methyl-benzaldehyde 
• 3644-91-5 (4-methylphenyl)triethylsilane 
• 99-75-2 4-methyl-benzoic acid methyl ester 
• 3287-02-3 4-(phenylethynyl)toluene 
• 82404-39-5 1-(4-methylphenyl)-2-(4-trifluoromethylphenyl)acetylene 
• 17537-45-0 N-(p-methylbenzoyl)-α-methylbenzyl amine 
• 195062-57-8 p-tolylboronic pinacol ester 
• 1325725-65-2 (R)-3-(4-methylbenzoyl)-3-phenyldihydrofuran-2(3H)-one 

Relevant academic research and scientific papers

MILD CONVERSION OF PRIMARY ALCOHOLS AND ALDEHYDES TO ACID FLUORIDES WITH CAESIUM FLUOROXYSULPHATE

Caesium fluoroxysulphate in acetonitrile medium at 35 deg C converts primary alcohols and alkyl, as well as aryl aldehydes, to acid fluorides in high yield.

Perfluoroalkyl Cobalt(III) Fluoride and Bis(perfluoroalkyl) Complexes: Catalytic Fluorination and Selective Difluorocarbene Formation

Four perfluoroalkyl cobalt(III) fluoride complexes have been synthesized and characterized by elemental analysis, multinuclear NMR spectroscopy, X-ray crystallography, and powder X-ray diffraction. The remarkable cobalt fluoride 19F NMR chemical shifts (-716 to -759 ppm) were studied computationally, and the contributing paramagnetic and diamagnetic factors were extracted. Additionally, the complexes were shown to be active in the catalytic fluorination of p-toluoyl chloride. Furthermore, two examples of cobalt(III) bis(perfluoroalkyl)complexes were synthesized and their reactivity studied. Interestingly, abstraction of a fluoride ion from these complexes led to selective formation of cobalt difluorocarbene complexes derived from the trifluoromethyl ligand. These electrophilic difluorocarbenes were shown to undergo insertion into the remaining perfluoroalkyl fragment, demonstrating the elongation of a perfluoroalkyl chain arising from a difluorocarbene insertion on a cobalt metal center. The reactions of both the fluoride and bis(perfluoroalkyl) complexes provide insight into the potential catalytic applications of these model systems to form small fluorinated molecules as well as fluoropolymers.

Fluoride complexes of cyclometalated iridium(III)

Many electroluminescent devices rely on cyclometalated iridium(III). Their advancement depends on access to reactive starting materials because of the inertness of Ir(III). Notably, fluoride complexes of bis(cyclometalated) Ir(III) are scarce. Syntheses of bridged and terminal fluorides are reported here. New compounds are luminescent and thermally reactive; they are characterized by ground-state and optical methods. Crystal structures were determined for one bridging and one terminal fluoride complex. The terminal fluoride shows intramolecular hydrogen bonding to an adjacent 3,5-dimethylpyrazole ligand; a lesser interaction may occur between F and a nearby aromatic C-H bond. Terminal fluoride complexes react with carbon-, silicon-, and sulfur-based electrophiles. The new complexes phosphoresce with microsecond lifetimes at 77 and 298 K. Density-functional theory calculations indicate triplet states with little contribution from fluoride. The compounds herein are versatile phosphors having the ground-state reactivity of late transition metal fluorides.

Acyl fluorides from carboxylic acids, aldehydes, or alcohols under oxidative fluorination

We describe a novel reagent system to obtain acyl fluorides directly from three different functional group precursors: carboxylic acids, aldehydes, or alcohols. The transformation is achieved via a combination of trichloroisocyanuric acid and cesium fluoride, which facilitates the synthesis of various acyl fluorides in high yield (up to 99%). It can be applied to the late-stage functionalization of natural products and drug molecules that contain a carboxylic acid, an aldehyde, or an alcohol group.

Carboxylic Acid Deoxyfluorination and One-Pot Amide Bond Formation Using Pentafluoropyridine (PFP)

This work describes the application of pentafluoropyridine (PFP), a cheap commercially available reagent, in the deoxyfluorination of carboxylic acids to acyl fluorides. The acyl fluorides can be formed from a range of acids under mild conditions. We also demonstrate that PFP can be utilized in a one-pot amide bond formation via in situ generation of acyl fluorides. This one-pot deoxyfluorination amide bond-forming reaction gives ready access to amides in yields of ≤94%.

Metal-free approach for hindered amide-bond formation with hypervalent iodine(iii) reagents: application to hindered peptide synthesis

A new bio-inspired approach is reported for amide and peptide synthesis using α-amino esters that possess a potential activating group (PAG) at the ester residue. To activate the ester functionality under mild metal-free conditions, we exploited the facile dearomatization of phenols with hypervalent iodine(iii) reagents. Using a pyridine-hydrogen fluoride complex, highly reactive acyl fluoride intermediates can be successfully generated, thereby allowing for the smooth formation of sterically hindered amides and peptides from bulky amines and α-amino esters, respectively.

Gram-Scale Preparation of Acyl Fluorides and Their Reactions with Hindered Nucleophiles

A series of acyl fluorides was synthesized at 100 mmol scale using phase-transfer-catalyzed halogen exchange between acyl chlorides and aqueous bifluoride solution. The convenient procedure consists of vigorous stirring of the biphasic mixture at room temperature, followed by extraction and distillation. Isolated acyl fluorides (usually 7-20 g) display excellent purity and can be transformed into sterically hindered amides and esters when treated with lithium amide bases and alkoxides under mild conditions.

N-Hydroxybenzimidazole as a structurally modifiable platform forN-oxyl radicals for direct C-H functionalization reactions

Methods for direct functionalization of C-H bonds mediated byN-oxyl radicals constitute a powerful tool in modern organic synthesis. While severalN-oxyl radicals have been developed to date, the lack of structural diversity for these species has hampered further progress in this field. Here we designed a novel class ofN-oxyl radicals based onN-hydroxybenzimidazole, and applied them to the direct C-H functionalization reactions. The flexibly modifiable features of these structures enabled facile tuning of their catalytic performance. Moreover, with these organoradicals, we have developed a metal-free approach for the synthesis of acyl fluoridesviadirect C-H fluorination of aldehydes under mild conditions.

Efficient cleavage of tertiary amide bonds: Via radical-polar crossover using a copper(ii) bromide/Selectfluor hybrid system

A novel approach for the efficient cleavage of the amide bonds in tertiary amides is reported. Based on the selective radical abstraction of a benzylic hydrogen atom by a CuBr2/Selectfluor hybrid system followed by a selective cleavage of an N-C bond, an acyl fluoride intermediate is formed. This intermediate may then be derivatized in a one-pot fashion. The reaction proceeds under mild conditions and exhibits a broad substrate scope with respect to the tertiary amide moiety as well as to nitrogen, oxygen, and carbon nucleophiles for the subsequent derivatization. Mechanistic studies suggest that the present reaction proceeds via a radical-polar crossover process that involves benzylic carbon radicals generated by the selective radical abstraction of a benzylic hydrogen atom by the CuBr2/Selectfluor hybrid system. Furthermore, a synthetic application of this method for the selective cleavage of peptides is described. This journal is

Halide-Accelerated Acyl Fluoride Formation Using Sulfuryl Fluoride

Herein, we report a new one-pot sequential method for SO2F2-mediated nucleophilic acyl substitution reactions starting from carboxylic acids. A mechanistic study revealed that SO2F2-mediated acid activation proceeds via the anhydride, which is then converted to the corresponding acyl fluoride. Tetrabutylammonium chloride or bromide accelerate the formation of acyl fluoride. Optimized halide-accelerated conditions were used to synthesize acyl fluorides in 30-80percent yields, and esters, amides, and thioesters in 72-96percent yields without reoptimization for each nucleophile.