100600-01-9

Upstream product

• 108-86-1 bromobenzene 
• 98-88-4 benzoyl chloride 
• 98-80-6 phenylboronic acid 
• 1739-18-0 [18O]phenol 
• 65-85-0 benzoic acid 
• 21048-30-6 ¹⁸O-benzoic acid 
• 13360-92-4 phenyl diphenylphosphinite 

Relevant academic research and scientific papers

Palladium-catalyzed aerobic oxidative coupling of acyl chlorides with arylboronic acids

The first example of a palladium-catalyzed aerobic oxidative coupling of acyl chlorides with arylboronic acids has been developed, leading to a wide range of aryl benzoates in good to excellent yields. This catalytic system shows broad functional group tolerance. Preliminary mechanistic experiments using deuterium labeling showed that the oxygen atom was derived from dioxygen. Copyright

Mechanically induced solvent-free esterification method at room temperature

Herein, we describe two novel strategies for the synthesis of esters, as achieved under high-speed ball-milling (HSBM) conditions at room temperature. In the presence of I2 and KH2PO2, the reactions afford the desired esterification derivatives in 45% to 91% yields within 20 min of grinding. Meanwhile, using KI and P(OEt)3, esterification products can be obtained in 24% to 85% yields after 60 min of grinding. In addition, the I2/KH2PO2 protocol was successfully extended to the late-stage diversification of natural products showing the robustness of this useful approach. Further application of this method in the synthesis of inositol nicotinate was also discussed. This journal is

Efficient method for the preparation of inverted alkyl carboxylates and phenyl carboxylates via oxidation-reduction condensation using 2,6-dimethyl-1,4-benzoquinone or simple 1,4-benzoquinone

Oxidation-reduction condensation using in situ formed alkoxydiphenylphosphines, 2,6-dimethy-1,4-benzoquinone, and carboxylic acids provides a useful method for the preparation of inverted tertiary alkyl carboxylates from the corresponding chiral tertiary alcohols under mild and neutral conditions. Similarly, it has afforded alkyl carboxylates successfully in good-to-high yields by the combined use of alkoxydiphenylphosphines having primary, secondary, or tertiary alkoxy groups, carboxylic acids, and simple 1,4-benzoquinone. When chiral secondary or tertiary alcohols are used, the corresponding inverted secondary or tertiary alkyl carboxylates are also obtained in good-to-high yields. In addition, a convenient method for the preparation of phenyl carboxylates in high yields has been established by utilizing oxidation-reduction condensation in toluene at 110 °C using phenoxydiphenylphosphines in situ-formed from phenols and chlorodiphenylphosphine, 2,6-dimethyl-1,4-benzoquinone, and carboxylic acids.

Aromatic Rearrangements in the Benzene Series. Part 3. Rearrangement of Isotopically Labelled Phenyl Benzoates: Intermolecularity of the ortho-Directed Rearrangement. Criteria for Determining the Intra-/Inter-molecularity of Aromatic Rearrangements

The rearrangement of a mixture of Ph13COOPh and PhCO18OPh (with some unlabelled ester) catalysed by anhydrous AlBr3 in homogeneous solution in chlorobenzene has been examined.Contrary to expectations, more of the 2-hydroxybenzophenone is formed intermolecularly than of the 4-hydroxybenzophenone at the beginning of the reaction, contradicting earlier views that a high ortho : para ratio in such reactions indicates the operation of an intramolecular mechanism.A mechanism is proposed for this stage of the rearrangement involving a cyclic six-membered transition state originating from one molecule of phenyl benzoate and one of Ph-C(OPh)=O+-Al-Br3, allowing C-acylation by the benzoyl moiety of the catalyst-ester complex to compete with bimolecular ester interchange.This C-acylation can only occur at the ortho-position of the phenoxy-ring of the (uncomplexed) ester molecule, because of steric requirements.This step of the rearrangement is thus necessarily intermolecular.Criteria for judging the intra- or inter-molecularity of aromatic rearrangements are also briefly discussed.