- Transition-Metal-Free DMAP-Mediated Aromatic Esterification of Amides with Organoboronic Acids
-
A new, transition-metal-free, effective method for aromatic esterification of amides with organoboronic acids has been developed. A wide range of benzoate derivatives were obtained with yields ranging from moderate to good. The catalytic reaction shows a broad substrate scope and excellent functional group tolerance. Conceptually, DMAP mediates the reaction and is crucial for this transformation.
- Guo, Jiarui,Liu, Lantao,Wang, Tao,Wang, Yanqing,Xu, Kai,Zhang, Yuheng
-
supporting information
p. 3274 - 3277
(2021/06/26)
-
- Ester Transfer Reaction of Aromatic Esters with Haloarenes and Arenols by a Nickel Catalyst
-
A catalytic ester transfer reaction of aromatic esters with aryl halides/arenols was developed. The present reaction can transfer an ester functional group from certain aromatic esters to haloarenes. This ester transfer reaction involves two oxidative additions-one from the C-C bond of the aromatic ester and one from the C-halogen bond of haloarenes-onto a nickel catalyst. The utilization of a Ni/dcypt catalyst capable of cleaving both chemical bonds was a key for the reaction progress. Furthermore, naphthol-based aryl electrophiles were also applicable to the catalytic system via C-O bond activation.
- Inayama, Naomi,Isshiki, Ryota,Muto, Kei,Yamaguchi, Junichiro
-
p. 3490 - 3494
(2020/03/23)
-
- Palladium-Catalyzed Aerobic Oxidative Coupling of Amides with Arylboronic Acids by Cooperative Catalysis
-
The first fluoride and palladium co-catalyzed conversion of amide to ester through an aerobic oxidative coupling pathway is reported. This new approach presents a practical process that employs easily available oxygen and commercially available arylboronic acids as coupling partners, uses a wide range of N- tosylamides, and proceeds under mild reaction conditions. This protocol demonstrates broad functional group tolerance, and provides an alternative option to synthesize esters from N-tosylamides which obtained by simply N-functionalization of secondary amides.
- Li, Yue,Wu, Hongxiang,Zeng, Zhuo
-
supporting information
p. 4357 - 4361
(2019/07/09)
-
- Base-Promoted Amidation and Esterification of Imidazolium Salts via Acyl C-C bond Cleavage: Access to Aromatic Amides and Esters
-
Imidazolium salts have been effectively employed as suitable acyl transfer agents in amidation and esterification in organic synthesis. The weak acyl C(O)-C imidazolium bond was exploited to generate acyl electrophiles, which further react with amines and alcohols to afford amides and esters. The broad substrate scope of anilines and benzylic amines and base-promoted conditions are the benefits of this route. Interestingly, phenol, benzylic alcohols, and a biologically active alcohol can also be subjected to esterification under the optimized conditions.
- Karthik, Shanmugam,Muthuvel, Karthick,Gandhi, Thirumanavelan
-
p. 738 - 751
(2019/01/24)
-
- Transesterification of (hetero)aryl esters with phenols by an Earth-abundant metal catalyst
-
Readily available and inexpensive Earth-abundant alkali metal species are used as efficient catalysts for the transesterification of aryl or heteroaryl esters with phenols which is a challenging and underdeveloped transformation. The simple conditions and the use of heterogeneous alkali metal catalyst make this protocol very environmentally friendly and practical. This reaction fills in the missing part in transesterification reaction of phenols and provides an efficient approach to aryl esters, which are widely used in the synthetic and pharmaceutical industry.
- Chen, Jianxia,Namila,Bai, Chaolumen,Baiyin, Menghe,Agula, Bao,Bao, Yong-Sheng
-
p. 25168 - 25176
(2018/07/29)
-
- Rhodium-catalysed aryloxycarbonylation of iodo-aromatics by 4-substituted phenols with carbon monoxide or paraformaldehyde
-
Rhodium-catalysed phenoxycarbonylation of aryl iodides were carried out under carbon-monoxide atmosphere and in the absence of CO, using paraformaldehyde as an alternative surrogate for carbonylation reactions. Both strategies proved to be efficient for the synthesis of the corresponding phenyl esters. High pressure reactions provided the ester products with good selectivity, however lower activity was achieved compared to palladium containing systems. Using paraformaldehyde as carbon-monoxide source special reaction conditions are required, thus dramatic changes observed during optimisation reactions. Using in situ generated Rh-diphosphine catalyst systems, remarkable influence of ligand structure and solvent composition was observed on the activity and chemoselectivity. The substrate scope and the substituent effect were also investigated.
- Seni, Anas Abu,Kollár, László,Mika, László T.,Pongrácz, Péter
-
-
- Palladium-Catalyzed Oxidative Carbonylation of Aryl Hydrazines with CO and O2 at Atmospheric Pressure
-
Palladium-catalyzed aerobic oxidative aminocarbonylation and alkoxycarbonylation reactions with aryl hydrazines as coupling partners have been developed. The oxidative carbonylation of aryl hydrazines proceeded smoothly at atmospheric pressure CO, employi
- Tu, Yongliang,Yuan, Lin,Wang, Tao,Wang, Changliu,Ke, Jiamei,Zhao, Junfeng
-
p. 4970 - 4976
(2017/05/12)
-
- Transition-Metal-Free Poly(thiazolium) Iodide/1,8-Diazabicyclo[5.4.0]undec-7-ene/Phenazine-Catalyzed Esterification of Aldehydes with Alcohols
-
Poly(3,4-dimethyl-5-vinylthiazolium) iodide was used as a polymer precatalyst in the presence of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) and phenazine for the oxidative esterification of aldehydes with alcohols. Selective functionalization of OH groups was achieved in the presence of NH2 groups. The poly(thiazolium) iodide/DBU/phenazine system exhibited excellent catalytic activity and could be reused five times without loss of activity.
- Chun, Supill,Chung, Young Keun
-
supporting information
p. 3787 - 3790
(2017/07/26)
-
- A facile, one-pot procedure for the conversion of aromatic aldehydes to esters, as well as thioesters and amides, via acyl hydrazide intermediates
-
Herein we present an efficient method for the synthesis of esters from aromatic aldehydes via readily accessible acyl hydrazides. The developed reaction protocol is shown to be tolerant of a range of aromatic aldehydes, bearing various functionalities, as well as being amenable to the synthesis of thioesters and amides.
- Maruani, Antoine,Lee, Maximillian T. W.,Watkins, George,Akhbar, Ahmed R.,Baggs, Henry,Shamsabadi, André,Richards, Daniel A.,Chudasama, Vijay
-
p. 3372 - 3376
(2016/01/16)
-
- Palladium-catalyzed non-directed C[sbnd]H benzoxylation of simple arenes with iodobenzene dibenzoates
-
A palladium-catalyzed non-directed C[sbnd]H benzoxylation of simple arenes with iodobenzene dibenzoates as both benzoxylate source and oxidant has been developed. The catalytic system was greatly promoted by a pyridine ligand. Good functional groups tolerance was showed in both hypervalent iodine reagents and arene substrates, which can be used for synthesis of aryl benzoates through simple aromatic compounds.
- Li, Li,Wang, Ying,Yang, Tingting,Zhang, Qian,Li, Dong
-
supporting information
p. 5859 - 5863
(2016/12/09)
-
- Palladium-catalyzed alkoxycarbonylation of aryl halides with phenols employing formic acid as the CO source
-
An efficient palladium-catalyzed alkoxycarbonylation of aryl halides with phenols has been developed. Various aryl benzoates have been isolated in good to excellent yields with formic acid as the CO source. The reaction proceeds smoothly under mild conditions and good functional group tolerance was observed.
- Qi, Xinxin,Li, Chong-Liang,Jiang, Li-Bing,Zhang, Wan-Quan,Wu, Xiao-Feng
-
p. 3099 - 3107
(2016/05/24)
-
- Direct esterification of aromatic aldehydes with tetraphenylphosphonium bromide under oxidative N-heterocyclic carbene catalysis
-
An unconventional reagent, tetraphenylphosphonium bromide, was employed as a phenyl source in the direct transformation of aromatic aldehydes to the corresponding phenyl esters under oxidative N-heterocyclic carbene (NHC) catalysis. The phenyl esters were obtained in moderate yields under mild and organocatalytic conditions. Copyright
- Ramanjaneyulu, Bandaru T.,Pareek, Manish,Reddy, Virsinha,Vijaya Anand
-
p. 431 - 437
(2014/04/03)
-
- Ligand-free palladium-catalyzed aerobic oxidative coupling of carboxylic anhydrides with arylboronic acids
-
We report a new, effective and environmentally friendly protocol for selective aerobic oxidative coupling of arylboronic acids with carboxylic anhydrides in the presence of ligand-free palladium catalyst. The aryl benzoates are obtained in good to excellent yields.
- Yin, Weiyan,He, Haifeng,Zhang, Yani,Long, Tong
-
p. 2402 - 2406
(2014/10/15)
-
- N-heterocyclic carbene-catalyzed oxidation of aldehydes for the synthesis of amides via phenolic esters
-
N-heterocyclic carbene-catalyzed oxidation using TEMPO is reported for the conversion of aldehydes to amides. A wide range of amides were synthesized in good yields (up to 72%) via a one-pot, sequential protocol involving oxidative esterification of aldehydes and subsequent aminolysis. To promote efficient aminolysis, various alkoxide leaving groups were evaluated.
- Ji, Miran,Lim, Seungyeon,Jang, Hye-Young
-
p. 28225 - 28228
(2014/07/22)
-
- Palladacycle-catalyzed carbonylation of aryl iodides or bromides with aryl formates
-
An efficient palladacycle-catalyzed aromatic carbonylation reaction of aryl formates with aryl iodides or bromides has been developed. Commercially available and easily prepared aryl formates were employed as carbonyl sources without the use of external carbon monoxide. The present catalytic system shows broad functional group tolerance and affords aryl benzoate derivatives in good to excellent yields. Copyright
- Chen, Guangwei,Leng, Yuting,Yang, Fan,Wang, Shiwei,Wu, Yangjie
-
p. 1488 - 1494
(2014/01/06)
-
- 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
- Chen, Jiuxi,Peng, Yong,Liu, Miaochang,Ding, Jinchang,Su, Weike,Wu, Huayue
-
supporting information
p. 2117 - 2122
(2012/11/07)
-
- N-heterocyclic carbene-catalyzed aerobic oxidative direct esterification of aldehydes with organoboronic acids
-
A simple procedure affording benzoates through a NHC-catalyzed aerobic oxidative esterification of aldehydes with organoboronic acids has been disclosed. This process allows access to a wide variety of aromatic esters in good to excellent yields under simple, efficient, and sustainable reaction conditions (see scheme).
- Meng, Jing-Jing,Gao, Min,Wei, Yu-Ping,Zhang, Wen-Qin
-
experimental part
p. 872 - 875
(2012/07/03)
-
- Radical OfC transposition: A metal-free process for conversion of phenols into benzoates and benzamides
-
We report a metal-free procedure for transformation of phenols into esters and amides of benzoic acids via a new radical cascade. Diaryl thiocarbonates and thiocarbamates, available in a single high-yielding step from phenols, selectively add silyl radicals at the sulfur atom of the CdS moiety. This addition step, analogous to the first step of the Barton-McCombie reaction, produces a carbon radical which undergoes 1,2 OfC transposition through an O-neophyl rearrangement. The usually unfavorable equilibrium in the reversible rearrangement step is shifted forward via a highly exothermic C-S bond scission in the O-centered radical, which furnishes the final benzoic ester or benzamide product. The metal-free preparation of benzoic acid derivatives from phenols provides a potentially useful alternative to metal-catalyzed carbonylation of aryl triflates.
- Baroudi, Abdulkader,Alicea, Jeremiah,Flack, Phillip,Kirincich, Jason,Alabugin, Igor V.
-
p. 1521 - 1537
(2011/06/11)
-
- NHC/Iron cooperative catalysis: Aerobic oxidative esterification of aldehydes with phenols
-
An NHC/iron cooperative catalytic system mediates the aerobic oxidative esterification of aldehydes with phenols. The use of equimolar amounts of reactants led to good to excellent isolated yields of esters.
- Reddy, R. Sudarshan,Rosa, Joao N.,Veiros, Luis F.,Caddick, Stephen,Gois, Pedro M. P.
-
supporting information; experimental part
p. 3126 - 3129
(2011/05/12)
-
- NHC-iron-catalyzed aerobic oxidative aromatic esterification of aldehydes using boronic acids
-
(Figure presented) NHC-iron complexes prepared in situ very efficiently afforded benzoates via the aerobic oxidative aromatic esterification of aldehydes with boronic acids. This method uses equimolar amounts of both the aldehyde and the boronic acid allo
- Rosa, Joao N.,Reddy, R. Sudarshan,Candeias, Nuno R.,Cal, Pedro M. S. D.,Gois, Pedro M. P.
-
supporting information; experimental part
p. 2686 - 2689
(2010/09/03)
-
- Radical 1,2-o→c transposition for conversion of phenols into benzoates by o-neophyl rearrangement/fragmentation cascade
-
Figure Presented Radical merry-go-round! Diaryl thiocarbonates, available in a single step from phenols, can be directly transformed into benzoates by a new radical cascade that transposes O and C atoms at the aromatic core. The cascade bypasses the common Barton McCombie fragmentation in favor of the usually unfavorable O-neophyl rearrangement, which is rendered irreversible and efficient by a highly exothermic C-S bond scission in the O-centered radical (see scheme; FG = functional group).
- Baroudi, Abdulkader,Alicea, Jeremiah,Alabugin, Igor Y.
-
experimental part
p. 7683 - 7687
(2010/08/22)
-
- A new versatile synthesis of esters from Grignard reagents and chloroformates
-
Cross-coupling reactions of chloroformates with organocopper reagents, derived from Grignard reagents, cuprous bromide and lithium bromide, provide a rapid and straightforward method for the synthesis of esters. Georg Thieme Verlag Stuttgart.
- Bottalico, Daniela,Fiandanese, Vito,Marchese, Giuseppe,Punzi, Angela
-
p. 974 - 976
(2008/02/02)
-
- Evaluation of antimycobacterial and anticonvulsant activities of new 1- (4-fluorobenzoyl)-4-substituted-thiosemicarbazide and 5-(4-fluorophenyl)-4- substituted-2,4-dihydro-3H,1,2,4-triazole-3-thione derivatives
-
Some new 1-(4-fluorobenzoyl)-4-alkyl/arylthiosemicarbazide (2a-g), 5- (4-fluorophenyl)4-alkyl/aryl-2,4-dihydr-3H-1,2,4-triazole-3-thione (3a-g) derivatives, 3-(benzylthio)-5-(4-fluorophenyl)-4-phenyl-4H-1,2,4-triazole (3h) and 2-acetyl-5-(4-fluorophenyl)-
- Gulerman,Rollas
-
p. 691 - 695
(2007/10/03)
-
- Preparation of 4-fluorophenol and 4-fluorobenzoic acid by the Baeyer-Villiger reaction
-
The possibility of preparing 4-fluorophenol or 4-fluorobenzoic acid via the Baeyer-Villiger reaction starting from unsymmetrical fluoroaryl ketones is disscussed.Several unsymmetrical 4-fluorobenzophenones having different substituents in the fluorine-free aryl group were prepared and converted to esters by treatment with peracetic acid.The electrophilicity of the substituents influenced the molecular structure of the ester formed as a result of a carbon-to-oxygen migration, and hence 4-fluorophenol or 4-fluorobenzoic acid formation.Electron-withdrawing substituents favoured the formation of 4-fluorophenol in good yields, while electron-donating substituents formed 4-fluorobenzoic acid preferentially.
- Conte, L.,Napoli, M.,Gambaretto, J. P.,Guerrato, A.,Carlini, F. M.
-
-