- Using Data Science To Guide Aryl Bromide Substrate Scope Analysis in a Ni/Photoredox-Catalyzed Cross-Coupling with Acetals as Alcohol-Derived Radical Sources
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Ni/photoredox catalysis has emerged as a powerful platform for C(sp2)–C(sp3) bond formation. While many of these methods typically employ aryl bromides as the C(sp2) coupling partner, a variety of aliphatic radical sources have been investigated. In principle, these reactions enable access to the same product scaffolds, but it can be hard to discern which method to employ because nonstandardized sets of aryl bromides are used in scope evaluation. Herein, we report a Ni/photoredox-catalyzed (deutero)methylation and alkylation of aryl halides where benzaldehyde di(alkyl) acetals serve as alcohol-derived radical sources. Reaction development, mechanistic studies, and late-stage derivatization of a biologically relevant aryl chloride, fenofibrate, are presented. Then, we describe the integration of data science techniques, including DFT featurization, dimensionality reduction, and hierarchical clustering, to delineate a diverse and succinct collection of aryl bromides that is representative of the chemical space of the substrate class. By superimposing scope examples from published Ni/photoredox methods on this same chemical space, we identify areas of sparse coverage and high versus low average yields, enabling comparisons between prior art and this new method. Additionally, we demonstrate that the systematically selected scope of aryl bromides can be used to quantify population-wide reactivity trends and reveal sources of possible functional group incompatibility with supervised machine learning.
- Doyle, Abigail G.,Gandhi, Shivaani S.,Jiang, Shutian,Kariofillis, Stavros K.,Martinez Alvarado, Jesus I.,?urański, Andrzej M.
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supporting information
p. 1045 - 1055
(2022/01/19)
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- Electrochemical esterification via oxidative coupling of aldehydes and alcohols
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An electrolytic method for the direct oxidative coupling of aldehydes with alcohols to produce esters is described. Our method involves anodic oxidation in presence of TBAF as supporting electrolyte in an undivided electrochemical cell equipped with graphite electrodes. This method successfully couples a wide range of alcohols to benzaldehydes with yields ranging from 70 to 90%. The protocol is easy to perform at a constant voltage conditions and offers a sustainable alternative over conventional methods.
- Smeyne, Dylan,Verboom, Katherine,Bryan, Maria,LoBue, James,Shaikh, Abid
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supporting information
(2021/03/26)
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- A Straightforward Conversion of Activated Amides and Haloalkanes into Esters under Transition-Metal-Free Cs 2 CO 3 /DMAP Conditions
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The esterification of activated amides, N -acylsaccharins, under transition-metal-free conditions with good functional group tolerance has been developed, resulting in C-N cleavage leading to efficient synthesis of a variety of esters in moderate to good yields. This work demonstrates that esterification may proceed by using simple N -acylsaccharins, haloalkanes, and Cs 2 CO 3 as oxygen source.
- Chen, Liuqing,Gu, Ying,Jian, Junsheng,Liu, Yueping,Miao, Liqiong,Wang, Zijia,Zeng, Zhuo
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p. 4078 - 4084
(2019/10/28)
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- Method for generating ester through reaction of benzoyl chloride and halogenated hydrocarbon
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The invention discloses a method for generating ester through reaction of benzoyl chloride and halogenated hydrocarbon. According to the method, benzoyl chloride, halogenated hydrocarbon and carbonate which are reaction substrates are heated and stirred to react in the presence of a catalyst 4-dimethylaminopyridine (DMAP) in an air or inert gas atmosphere to generate a corresponding ester product. The method disclosed by the invention has the beneficial effects that benzoyl chloride, halogenated hydrocarbon and carbonate are taken as the reaction substrates for the first time, carbonate is found as a source of oxygen in the product for the first time, and the reaction is found as a free radical mechanism for the first time.
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Paragraph 0033; 0034; 0035
(2017/08/31)
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- An Effective Method for the Construction of Esters Using Cs2CO3 as Oxygen Source
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An effective method for the construction of esters from acyl chloride and halohydrocarbon using Cs2CO3 as an oxygen source was achieved for the first time. The methodology has a wide scope of substrates and can be scaled up. The study of a preliminary reaction mechanism demonstrated that the O in the products comes from Cs2CO3 and this esterification proceeds through a free radical reaction. It was also found that CO2 can also be used in this esterification reaction as an oxygen source.
- Ren, Lanhui,Wang, Lianyue,Lv, Ying,Li, Guosong,Gao, Shuang
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supporting information
p. 5172 - 5175
(2015/11/24)
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- Hydrogen peroxide mediated efficient amidation and esterification of aldehydes: Scope and selectivity
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An efficient method for the amidation and esterification of aldehydes utilizing hydrogen peroxide as an oxidant has been developed. Cyclic amines and primary alcohols selectively reacted with aromatic aldehydes under mild conditions to yield the corresponding amides and esters.
- Tank, Rekha,Pathak, Uma,Vimal, Manorama,Bhattacharyya, Shubhankar,Pandey, Lokesh Kumar
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p. 3350 - 3354
(2012/01/06)
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- Rate-acceleration in gold-nanocluster-catalyzed aerobic oxidative esterification using 1,2- and 1,3-diols and their derivatives
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Aerobic oxidation of aldehydes to 1,2- and 1,3-diol monoesters was catalyzed by polymer-incarcerated gold nanoclusters under ambient conditions. The esterification proceeded much faster with 1,2- and 1,3-diols and their derivatives rather than with methanol. Magnum PI: Gold-nanocluster catalysts, PI-Au, that were immobilized on polystyrene-based polymers with cross-linking moieties, were used to catalyze the syntheses of 1,2 and 1,3-diol monoesters and their derivatives from aldehydes. The effect of neighboring-group participation in the esterification reaction is also described. Copyright
- Yasukawa, Tomohiro,Miyamura, Hiroyuki,Kobayashi, Shu
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experimental part
p. 621 - 627
(2011/10/12)
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- Triphenylphosphine dibromide: a simple one-pot esterification reagent
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We report a one-pot, expedient protocol for the conversion of carboxylic acids to their esters using excess triphenylphosphine dibromide, base, and the alcohol. The reaction gave the esterified product in moderate-to-high yields (30-95%). For chiral acids, the reaction proceeded with little or no racemization. Use of a chiral alcohol in this transformation gave the ester with retention of configuration of the stereogenic center. Information is presented indicating that esterification proceeds through the intermediate generation of an acyloxyalkoxyphosphorane and where steric interactions play an important role in the energetics of the reaction.
- Salomé, Christophe,Kohn, Harold
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supporting information; experimental part
p. 456 - 460
(2009/04/06)
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- Group 5 and group 6 metal halides as very efficient catalysts for acylative cleavage of ethers
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Group 5 and 6 metal chlorides such as MoCl5, WCl6, NbCl5 and TaCl5 were found as very efficient catalysts for acylative cleavage of the C-O bond of ethers. Compared with conventional Lewis acid catalysts such as ZnCl2, AlCl3, SnCl4 and TiCl4, group 5 and 6 metal chlorides showed better results in the catalytic C-O bond cleavage of dibutyl ether with benzoyl chloride.
- Guo, Qiaoxia,Miyaji, Taichi,Hara, Ryuichiro,Shen, Baojian,Takahashi, Tamotsu
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p. 7327 - 7334
(2007/10/03)
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- Direct transacylation of 2,2,2-trihaloethyl esters with amines and alcohols using phosphorus(III) reagents for reductive fragmentation and in situ activation
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Amides and esters have been synthesized from 2,2,2-trihaloethyl esters in one pot using phosphorus(III) reagents as reductants, with resultant carboxylate activation as an acyloxyphosphonium intermediate, and in situ trapping by amine or alcohol nucleophiles. Secondary and tertiary amides were synthesized, including a dipeptide, in good yields using hexamethylphosphorous triamide, (Me2N)3P, as reducing agent. Optimal yields of esters derived from primary and secondary alcohols were obtained using tributylphosphine and DMAP. Tribromoethyl esters provided yields superior to those obtained with trichloroethyl esters.
- Hans, Jeremy J.,Driver, Russell W.,Burke, Steven D.
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p. 2114 - 2121
(2007/10/03)
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- A New Indirect Application of Aggregative Activation: Synthesis of Esters by Cobalt-Catalyzed Carbonylation of Aryl, Heterocyclic, and Vinyl Halides under Atmospheric Pressure
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Sun lamp illuminated alkoxycarbonylation of aryl, heteroaryl, and vinyl halides was performed under atmospheric pressure of CO in the presence of a cobalt catalyst in situ generated from Co(OAc)2.Illunination through a Pyrex flask was sufficient to catalyze the reaction.This process avoids the use of Co2(CO)8 and excess CH3I, which were required in the earlier procedure.A SRN1 mechanism is proposed.
- Marchal, Joel,Bodiguel, Jacques,Fort, Yves,Caubere, Paul
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p. 8336 - 8340
(2007/10/02)
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- REACTION OF DIOLS AND TRIOLS WITH TRIALKYL ORTHOESTERS: FACILE ONE-POT FORMATION OF OXACYCLIC COMPOUNDS FROM TRIOLS
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Reaction of diols and triols with trialkyl orthoesters was studied and facile one-pot formation of oxacyclic compounds from triols was developed.
- Fujioka, Hiromichi,Kitagawa, Hidetoshi,Kondo, Michinori,Matsunaga, Naoki,Kitagaki, Shinji,Kita, Yasuyuki
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p. 665 - 669
(2007/10/02)
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- Cobalt(II) catalyzed oxidation of 2-substituted 1,3-dioxolanes with molecular oxygen
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Cobalt(II) chloride catalyzed oxidation of 2-substituted 1,3-dioxolanes in 1,2-dimethoxyethane afforded formate esters and acids in high yields.Is was found that the presence of catalytic amounts of ZnCl2 increased the rate of oxidation.A free-radical mechanism is proposed, involving participation of superoxocobalt, and the esterification of the alcohol and acid.
- Li, Pei,Alper, Howard
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- N-Acyltetrazole as an intermediate for preparation of carboxylic acid derivatives
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A new mild and very efficient procedure for preparation of acid derivatives via N-acyl-5-phenyltetrazole is reported. The yields are high at -10°C and purification is simple but, because of the thermal instability of the intermediate, a certain amount of corresponding oxadiazole arises if the reaction is carried out at higher temperature.
- Jursic
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p. 361 - 364
(2007/10/02)
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