- Effect of nucleophile on the activation parameters of transesterification of 4-nitrophenyl benzoates
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Activation parameters of the reaction of 4-nitrophenyl benzoates with benzenethiol in the presence of potassium carbonate in dimethylformamide were determined. The entropies of activation for the reactions of unsubstituted 4-nitrophenyl benzoate and 4-nit
- Os'kina,Vlasov
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- Rh(I)-Catalyzed Intramolecular Decarbonylation of Thioesters
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Decarbonylative synthesis of thioethers from thioesters proceeds in the presence of a catalytic amount of [Rh(cod)Cl]2 (2 mol %). The protocol represents the first Rh-catalyzed decarbonylative thioetherification of thioesters to yield valuable thioethers. Notable features include the absence of phosphine ligands, inorganic bases, and other additives and excellent group tolerance to aryl chlorides and bromides that are problematic using other metals to promote decarbonylation. Gram scale synthesis, late-stage pharmaceutical derivatization, and orthogonal site-selective cross-couplings by C-S/C-Br cleavage are reported.
- Cao, Han,Liu, Xuejing,Bie, Fusheng,Shi, Yijun,Han, Ying,Yan, Peng,Szostak, Michal,Liu, Chengwei
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p. 10829 - 10837
(2021/07/28)
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- Visible-Light-Mediated Cross Dehydrogenative Coupling of Thiols with Aldehydes: Metal-Free Synthesis of Thioesters at Room Temperature
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Thioesters play a crucial role in biological systems and serve as important building blocks for organic synthesis. Herein, Eosin Y and TBHP mediated photochemical cross dehydrogenative coupling (PCDC) between feedstock aldehydes and thiols has been descri
- Roy, Vishal Jyoti,Sen, Partha Pratim,Raha Roy, Sudipta
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p. 16965 - 16976
(2021/11/18)
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- Thioesterification and Selenoesterification of Amides via Selective N-C Cleavage at Room Temperature: N-C(O) to S/Se-C(O) Interconversion
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The direct nucleophilic addition to amides represents an attractive methodology in organic synthesis that tackles amidic resonance by ground-state destabilization. This approach has been recently accomplished with carbon, nitrogen and oxygen nucleophiles.
- Li, Guangchen,Rahman, Md. Mahbubur,Szostak, Michal
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supporting information
p. 1060 - 1066
(2020/04/01)
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- Decarbonylative thioetherification by nickel catalysis using air- and moisture-stable nickel precatalysts
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A general, highly selective method for decarbonylative thioetherification of aryl thioesters by C-S cleavage is reported. These reactions are promoted by a commercially-available, user-friendly, inexpensive, air- and moisture-stable nickel precatalyst. The process occurs with broad functional group tolerance, including free anilines, cyanides, ketones, halides and aryl esters, to efficiently generate thioethers using ubiquitous carboxylic acids as ultimate cross-coupling precursors (cf. conventional aryl halides or pseudohalides). Selectivity studies and site-selective orthogonal cross-coupling/thioetherification are described. This thioester activation/coupling has been highlighted in the expedient synthesis of biorelevant drug analogue. In light of the synthetic utility of thioethers and Ni(ii) precatalysts, we anticipate that this user-friendly method will be of broad interest.
- Liu, Chengwei,Szostak, Michal
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supporting information
p. 2130 - 2133
(2018/03/06)
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- Syntheses of thiol and selenol esters by oxidative coupling reaction of aldehydes with RYYR (Y = S, Se) under metal-free conditions
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Thiol and selenol esters were synthesized by a direct oxidative coupling reaction of aldehydes with disulfides or diselenides in ethyl acetate under metal-free conditions. Among the oxidants examined, tert-butyl peroxide (TBP) was shown to give the best results. For the substrates with both electron-donating and electron-withdrawing substituents, the reaction proceeded smoothly and gave moderate to good yields. Compared with the previous method, the present route is very simple, atom-economical and environmentally friendly. This journal is the Partner Organisations 2014.
- He, Chunhuan,Qian, Xuewei,Sun, Peipei
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supporting information
p. 6072 - 6075
(2014/08/05)
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- Pd-catalyzed thiocarbonylation with stoichiometric carbon monoxide: Scope and applications
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A general protocol for the Pd-catalyzed thiocarbonylation of aryl iodides with stoichiometric carbon monoxide has been established employing a catalytic system composed of Pd(OAc)2 and DPEphos with low catalyst loading (1 mol %). Both electron-rich and -deficient aryl iodides proved effective for these couplings with aryl and alkyl thiols. The choice of the metal ligands and the solvent system was crucial for the efficiency and chemoselectivity of these transformations.
- Burhardt, Mia N.,Taaning, Rolf H.,Skrydstrup, Troels
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supporting information
p. 948 - 951
(2013/03/28)
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- Kinetics of the reaction of substituted 4-nitrophenyl benzoates with benzenethiol in the presence of potassium carbonate in dimethylformamide
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The effect of the substituent nature on the rate and activation parameters of transesterification of a series of 4-nitrophenyl benzoates with benzenethiol in dimethylformamide in the presence of potassium carbonate was studied by the competing reaction method. In all cases, change of the Gibbs energy of activation is determined mainly by variation of the enthalpy of activation. 4-Nitrophenyl benzoates having electron-withdrawing substituents in the benzoyl fragment were found to fit an isokinetic relation with an isokinetic temperature β of 318 K. Enthalpy-entropy compensation effect was observed in the reactions with all the examined 4-nitrophenyl benzoates. The relation between the reactivity and polarizability of nucleophilic center in S-and O-nucleophiles is discussed.
- Os'kina,Vlasov
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experimental part
p. 561 - 569
(2009/04/05)
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- A New and Efficient Esterification Reaction via Mixed Anhydrides by the Promotion of a Catalytic Amount of Lewis Acid
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In the presence of a catalytic amount of Lewis acid, various carboxylic esters or S-phenyl carbothioates are prepared in excellent yields by the respective reactions of equimolar amounts of silyl carboxylates and alkyl silyl ethers or phenyl silyl sulfides with 4-trifluoromethylbenzoic anhydride.
- Miyashita, Mitsutomo,Shiina, Isamu,Miyoshi, So,Mukaiyama, Teruaki
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p. 1516 - 1527
(2007/10/02)
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