Phenyl Formate Research Articles

Practical Synthesis of Axially Chiral Dicarboxylates via Pd-Catalyzed External-CO-Free Carbonylation.

We have developed a safe and practical synthetic method for preparing axially chiral diphenyl dicarboxylates using Pd-catalyzed external-CO-free carbonylation with phenyl formate as a CO surrogate. Optimized conditions consisted of axially chiral [1,1'-binaphthalene]-2,2'-diyl ditriflate and its congeners, each easily prepared from commercially available enantiomerically pure diols, Pd(OAc)2, 1,3-bis(diphenylphosphino)propane, ethyldiisopropylamine, and no solvent. To demonstrate the potential utility of these products, this method was conducted on gram-scale and the phenyl ester products were converted to other useful compounds, and both processes were carried out without difficulty.

Pd-Catalyzed regioselective hydroesterification of 2-allylphenols to seven-membered lactones without external CO gas.

Effective Pd-catalyzed regioselective hydroesterification of 2-allylphenols with phenyl formate is described. A variety of seven-membered lactones can be obtained in good yields under mild conditions without the use of toxic CO gas.

ChemInform Abstract: Pd‐Catalyzed Regiodivergent Hydroesterification of Aryl Olefins with Phenyl Formate.

AbstractDependent on the choice of ligand, either linear or branched phenyl arylpropanoates are selectively obtained.

Palladium-Catalyzed Carbonylative Annulation Reactions Using Aryl Formate as a CO Source: Synthesis of 2-Substituted Indene-1,3(2H)-dione Derivatives.

An efficient synthesis of 2-substituted indene-1,3(2H)-diones from stable and readily available 1-(2-halophenyl)-1,3-diones by employing phenyl formate as a CO source has been developed. The reaction occurred via palladium-catalyzed intramolecular carbonylative annulation using K3PO4 as a base and DMSO as a solvent at 95 °C. In this protocol, the reaction showed a broad substrate scope with good to excellent yields.

ChemInform Abstract: Carbonylative Synthesis of Phthalimides and Benzoxazinones by Using Phenyl Formate as a Carbon Monoxide Source.

A simple and efficient palladium-catalyzed carbonylative cyclization of N-substituted 2-iodobenzamides and 2-iodoanilides was investigated for the synthesis of phthalimides and benzoxazinones, respectively, by using phenyl formate as a CO source. The present catalytic protocol circumvents the use of an expensive phosphine ligand as well as solvent in the case of the phthalimide synthesis. Moreover, mild reaction conditions and a tolerance of various functional groups enhance the general applicability of this method.

Pd-Catalyzed Regiodivergent Hydroesterification of Aryl Olefins with Phenyl Formate.

An effective Pd-catalyzed regiodivergent hydroesterification of aryl olefins with phenyl formate is described. Either linear or branched phenyl arylpropanoates can be obtained in good yields with high regioselectivities by the judicious choice of ligand without the use of toxic CO gas.

ChemInform Abstract: Concise Synthesis of Cyclic Carbonyl Compounds from Haloarenes Using Phenyl Formate as the Carbonyl Source.

Various cyclic carbonyl compounds were concisely synthesized by carbonylative cyclization of haloarenes bearing nucleophilic moieties under Pd catalysis. A broad substrate scope and a feasible large-scale synthesis clearly demonstrate the high applicability of the reaction as a general, user-friendly method for access to cyclic carbonyl compounds.

ChemInform Abstract: Nickel(0)‐Catalyzed [2 + 2 + 1] Carbonylative Cycloaddition of Imines and Alkynes or Norbornene Leading to γ‐Lactams.

AbstractA key feature of the process is the use of phenyl formate as a CO source that enables carbonylation and prevents quenching of the catalyst.

ChemInform Abstract: Facile Palladium‐Catalyzed Hydrocarboxylation of Olefins Without External CO Gas.

AbstractThe facile protocol allows the hydrocarbonylation of olefins with phenyl formate and formic acid to afford carboxylic acids with high regioselectivity.

Carbonylative Synthesis of Phthalimides and Benzoxazinones by Using Phenyl Formate as a Carbon Monoxide Source

AbstractA simple and efficient palladium‐catalyzed carbonylative cyclization of N‐substituted 2‐iodobenzamides and 2‐iodoanilides was investigated for the synthesis of phthalimides and benzoxazinones, respectively, by using phenyl formate as a CO source. The present catalytic protocol circumvents the use of an expensive phosphine ligand as well as solvent in the case of the phthalimide synthesis. Moreover, mild reaction conditions and a tolerance of various functional groups enhance the general applicability of this method.

The Power of Nonconventional Phenyl C–H···N Hydrogen Bonds: Supportive Crystal-Packing Force and Dominant Supramolecular Engineering Force

The role of phenyl C–H···N interactions in crystal engineering is explored with a variety of fluorinated phenyl-containing compounds. In particular, we show that this interaction can guide the formation of one-dimensional phenyl C–H···N hydrogen-bonded ribbons with, for example, 4-(2,3,5,6-tetrafluorophenylethynyl)pyridine. The interaction is shown to also control the formation of self-complementary homodimers with 3-(2,3,4,5-tetrafluorophenylethynyl)pyridine. We also demonstrate that the phenyl C–H···N hydrogen bond interaction is capable of enticing co-crystallization of molecules such as 2,3,5,6,2′,3′,5′,6′-octafluorobiphenyl and 4,4′-dipyridyl. Finally, we describe the use of an intramolecular scaffold to evaluate the effect of electron-withdrawing substituents on the strength of a phenyl C–H···N hydrogen bond.

Degradation and kinetics of phenoxyacetic acid in aqueous solution by ozonation

This study aims to investigate degradation mechanisms and kinetics of phenoxyacetic acid by ozonation in aqueous solution. The optimized operating condition was achieved by phenoxyacetic acid and total organic carbon (TOC) removal based on the studies of the effects of various parameters, such as pH value (4–12), the initial concentration of phenoxyacetic acid (100–2000mgL−1) and the ozone dosage (16–48mgmin−1). A series of intermediates were formed in the ozonation process and detected by GC/MS and HPLC analysis, such as phenyl formate, salicylic acid, phenol, oxalic acid and small molecule acids. A possible degradation pathway of phenoxyacetic acid was proposed. The kinetic analysis showed that phenoxyacetic acid degradation was in slow kinetic regime based on the results of Ha. This paper can provide basic data and theoretical reference for pharmaceutical wastewater treatment by ozonation.

A palladium-catalyzed enantioselective hydroesterification of alkenylphenols with phenyl formate. A facile approach to optically active dihydrocoumarins.

An effective palladium-catalyzed enantioselective hydroesterification of alkenylphenols with phenyl formate as a CO source is described. A variety of optically active dihydrocoumarins can be obtained in generally high yields with up to 91% ee.

Concise synthesis of cyclic carbonyl compounds from haloarenes using phenyl formate as the carbonyl source.

Various cyclic carbonyl compounds were concisely synthesized by carbonylative cyclization of haloarenes bearing nucleophilic moieties under Pd catalysis. A broad substrate scope and a feasible large-scale synthesis clearly demonstrate the high applicability of the reaction as a general, user-friendly method for access to cyclic carbonyl compounds.

ChemInform Abstract: Formic Acid Derivatives as Practical Carbon Monoxide Surrogates for Metal‐Catalyzed Carbonylation Reactions

AbstractReview: [40 refs.

Facile palladium-catalyzed hydrocarboxylation of olefins without external CO gas.

An effective Pd-catalyzed hydrocarboxylation of olefins with phenyl formate and formic acid is described. A variety of carboxylic acids are obtained in good yields with high regioselectivities under operationally simple conditions without the use of toxic CO gas.

Nickel(0)-catalyzed [2 + 2 + 1] carbonylative cycloaddition of imines and alkynes or norbornene leading to γ-lactams.

The first nickel(0)-catalyzed [2 + 2 + 1] carbonylative cycloaddition reaction of imines and alkynes or norbornene has been achieved by employing phenyl formate as a CO source. With this method, a variety of N-benzenesulfonyl, -tosyl, and -phosphoryl-substituted γ-lactams can be prepared in good to high yields.

ChemInform Abstract: Aryl Formate as Bifunctional Reagent: Applications in Palladium‐Catalyzed Carbonylative Coupling Reactions Using in situ Generated CO.

AbstractThe carbonylative reactions rely on the cooperation between phenyl formate and nonaflate and the generation of CO in situ by using aryl formates as the CO source and pseudohalide precursors.

Formic Acid Derivatives as Practical Carbon Monoxide Surrogates for Metal-Catalyzed Carbonylation Reactions

This account describes our findings on formic acid derivatives as practical carbon monoxide (CO) surrogates in synthetic organic chemistry. Among the known CO surrogates, formic acid derivatives are advantageous in terms of their good availability, stability, and ease of handling. We adopted two approaches to expand the synthetic utility of formic acid derivatives. One is the use of formic acid esters for reactions with alkenes based on the finding that substituted imidazoles can function as the ligands in ruthenium-catalyzed hydroesterifications of alkenes. The other approach involves the use of formic acid derivatives for reactions with (hetero)aryl or alkenyl halides based on the finding that phenyl formate undergoes decomposition to give CO and phenol by simply reacting with a weak base such as triethylamine. In addition to phenyl formate, electrophilic formic acid derivatives such as 2,4,6-trichlorophenyl formate and N-formylsaccharin were found to be stable on storage, but highly reactive, even under ambient reaction conditions, functioning as CO-generating compounds. The in situ generated CO can be incorporated efficiently into products under metal catalysis, thus providing a novel carbonylation. Notably, the carbonylation process did not require the use of external gaseous CO, thus significantly enhancing the safety and practicality of the approach. 1 Introduction 2 Ruthenium-Catalyzed Hydroesterification 3 Palladium-Catalyzed Aryloxycarbonylation 3.1 Decomposition of Phenyl Formate under Weakly Basic Conditions 3.2 Aryloxycarbonylation Using Phenyl Formate 3.3 Room-Temperature Aryloxycarbonylation Using 2,4,6-Trichlorophenyl Formate 4 Reductive Carbonylation Using N-Formylsaccharin 5 Fluorocarbonylation Using N-Formylsaccharin 6 Conclusion

ChemInform Abstract: A Palladium‐Catalyzed Regioselective Hydroesterification of Alkenylphenols to Lactones with Phenyl Formate as CO Source.

An effective Pd(OAc)2-PPh3 catalyzed hydroesterification of alkenylphenols with phenyl formate as CO surrogate is described. A variety of lactones are obtained in generally high yields with high regioselectivities. In one case, 76% ee is obtained with a chiral ligand.