A green and highly efficient alkylation of thiols in water

An environmentally benign and efficient process for the preparation of thioethers was developed by simple and practical reactions of alkyl halides and thiols in water in the presence of K₂CO₃ or Et₃N in very high yields. The reaction of aryl, alkyl, aliphatic and hindered thiols with various alkyl halides gave the corresponding products with significant advantages such as high conversions, short reaction time, mild reaction conditions, and low cost, simple workup with good to quantitative yields.     

Synthesis of alkenyl sulfides through the iron-catalyzed cross-coupling reaction of vinyl halides with thiols

We report here the iron-catalyzed cross-coupling reaction of alkyl vinyl halides with thiols. While many works are devoted to the coupling of thiols with alkyl vinyl iodides, interestingly, the known S-vinylation of vinyl bromides and chlorides is limited to 1-(2-bromovinyl)benzene and 1-(2-chlorovinyl)benzene. Investigation on the coupling reaction of challenging alkyl vinyl bromides and chlorides with thiols is rare. Since the coupling of 1-(2-bromovinyl)benzene and 1-(2-chlorovinyl)benzene with thiols can be performed in the absence of any catalyst, here we focus on the coupling of thiols with alkyl vinyl halides. This system is generally reactive for alkyl vinyl iodides and bromides to provide the products in good yields. 1-(Chloromethylidene)-4-tert-butyl-cyclohexane was also coupled with thiols, giving the targets in moderate yields.     

Triton B–Mediated Mild,Convenient, and Efficient Method for the Selective Alkylation of Cyclic Secondary Amines and Thiols

Alkylation of cyclic secondary amines, thiols, and pyridazinones has been demonstrated with alkyl halides using Triton B as base and reaction medium.     

Indium(I) iodide-promoted cleavage of diaryl diselenides and disulfides and subsequent condensation with alkyl or acyl halides. One-pot efficient synthesis of diorganyl selenides, sulfides, selenoesters, and thioesters

Diphenyl diselenides and disulfides undergo facile cleavages by indium(I) iodide and the corresponding generated selenate and thiolate anions condense in situ with alkyl or acyl halides present in the reaction mixture. Thus, a simple, efficient, and general procedure has been developed for the synthesis of unsymmetrical diorganyl selenides, sulfides (thioethers), selenoesters, and thioesters by this one-pot reaction at room temperature.     

Sodium Hydroxide (NaOH)-Mediated Oxidative Hydroxylation of Arylboronic Acids and Its Applications in C-O Bond Formation

We have developed a straightforward methodology for converting arylboronic acids into phenols using NaOH-mediated air oxidation. This reaction offers several advantages, including simple operation, excellent tolerance towards various functional groups, and scalability. The transmetalation of the resulting borate ester with NaOH occurs readily, enabling convenient derivatization of the borate ester into aryl ethers and esters using alkyl and acyl halides.     

Copper‐Catalyzed Cross‐CouplingLigand‐Free Conditions Reaction of Thiols with Aryl Iodides under

Commercially available CuO powder is found to be a suitable catalyst for C‐S coupling reaction between aryl‐ and alkyl thiols and aryl iodides. Functional groups including halides, ketone, unprotected amine and heterocycles were tolerated by the reaction conditions employed.     

A facile one-pot synthesis of N-substituted tetrahydroquinolines

An uncatalyzed one-pot synthesis of N-substituted tetrahydroquinolines was achieved in good yields by the reaction of quinoline and alkyl/acyl halides with Hantzsch dihydropyridine ester under mild reaction conditions.     

钯催化Stille交叉偶联反应研究新进展

综述了钯催化Stille交叉偶联反应的最新研究进展, 主要包括三个方面: (1)有机锡化合物与有机亲电试剂如卤代芳香烃、卤代烷烃、酰氯等的反应; (2)Stille反应的机理; (3) Stille反应在有机合成中的应用.     

Rhodium-catalyzed reductive coupling of disulfides and diselenides with alkyl halides, using hydrogen as a reducing agent

[reaction: see text] We have established that RhCl(PPh3)3 catalyzes a reductive coupling of disulfides and diselenides with alkyl halides in the presence of triethylamine using hydrogen as a reducing agent. This reaction serves as a convenient new method to produce unsymmetrical sulfides and selenides from disulfides and diselenides instead of unstable and odoriferous thiols and selenols.     

SYNTHESIS OF SELENOL ESTERS USING ACYL HALIDES AND A NOVEL SELENATING REAGENT,LiAlHSeH

Several selenol esters were synthesized by the reaction of acyl chlorides with LiAlHSeH then with alkyl halides in moderate to good yields.     

Influence of catalytic system composition on formation of adamantane containing ketones

The preparation of non-symmetrical ketones by the reaction of acyl chlorides and the corresponding Grignard reagents in the presence of catalytic amounts of metal halides is described. The composition of catalyst has a great influence on the yield of the required ketone as well as on side product formation. For each catalytic system, the yield of ketone and the number of side products changes with the time of addition of the Grignard reagent. We examined the influence of both factors in our model reaction of adamantane-1-carbonyl chloride with ethylmagnesium bromide and discussed the possible mechanisms from this point of view. We have found ZnCl₂, MnCl₂, AlCl₃ and CuCl to be active catalytic components and developed very efficient, cheap and fast methods for the preparation of alkyl adamantyl ketones. The procedure was also tested for the synthesis of other alkyl aryl ketones.     

Simple Method for the Preparation of Symmetrical Alkyl and Aryl Disulfides with Alkyl Sulfonyl Halides in Nitrogenous Base

In the present study, the reaction of thiols with alkyl sulfonyl halides was carried out in a nitrogenous base to compare the reactivity of ‐SH with that of ‐OH, which, however, led to the formation of disulfides. The reaction achieved as a result offers the use of an inexpensive reagent, quantitative yields of the product, and simplicity for the formation of the S‐S bond.     

Cyclopropyl organyl sulfides

Conclusions Three methods were developed for the synthesis of cyclopropyl organyl sulfides, which are based on the reaction of cyclopropyl halides with either thiols or alkali metal thiolates in a superbasic medium, the reaction of cyclopropyllithium with diorganyl disulfides, and the reaction of cyclopropyl alkyl sulfides with lithium in liquid ammonia and subsequent reaction with organic bromo derivatives. In contrast, the cleavage of cyclopropyl aryl sulfides leads to the formation of lithium arylthiolates.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 1, pp. 1664–1667, July, 1983.     

Nickel or Palladium‐Catalyzed Decarbonylative Transformations of Carboxylic Acid Derivatives

Carboxylic acid derivatives containing acyl halides, anhydrides, esters, amides and acyl nitriles are highly appealing electrophiles in transition‐metal‐catalyzed carbon‐carbon bond‐forming reactions due to their ready availability and low cost, which can provide divergent transformations of carboxylic acids into other value‐added products. In this Minireview, we focus on the recent advances of decarbonylative transformations of carboxylic acid derivatives in carbon‐carbon bond formations using Ni or Pd catalysts. A series of reaction types, product classifications and reaction pathways are presented herein, which show the advantageous features of carboxylic acid derivatives as alternative to aryl or alkyl halides in terms of reactivity and compatibility. The well‐accepted mechanism of nickel‐ or palladium‐catalyzed decarbonylative transformations involves initial oxidative addition of carboxylic acid derivatives, followed by decarbonylation or transmetalation (or insertion), and reductive elimination to generate the products, thereby regenerating the catalysts.     

Cyanogen Bromide Promoted Thiol Dimerization

The synthesis of alkyl thiocyanates by the reaction of thiols with cyanogen chloride has been known,¹ although it is generally supersede by the more convenient displacement of alkyl halides with alkali thio-cyanates.² We wish to describe the behavior of sodium thiolates toward cyanogen bromide.     

Synthesis of Thiols via Palladium Catalyzed Methanolysis of Thioacetates with Borohydride Exchange Resin

Various thiols are prepared quantitatively from the corresponding thioacetates via Pd catalyzed methanolysis with borohydride exchange resin under a mild and neutral conditions. One-pot synthesis of thiols from alkyl halides through the formation of alkyl thioacetates using thioacetate exchange resin followed by methanolysis is also described.     

Iron-catalyzed Grignard cross-coupling with alkyl halides possessing beta-hydrogens

Tris(acetylacetonato)iron(III) (Fe(acac)(3)) was found to be an efficient catalyst for the cross-coupling reaction between aryl Grignard reagents and alkyl halides possessing beta-hydrogens. The reaction is applicable to secondary alkyl halides as well as primary ones. [reaction: see text]     

Free-Radical Carbonylations: Then and Now

Although known since the 1950s, free-radical carbonylation has not received much attention until only recently. In the last few years the application of modern free-radical techniques has revealed the high synthetic potential of this reaction as a tool for introducing CO into organic molecules. Clearly now is the time for a renaissance of this chemistry. Under standard conditions (tributyltin hydride/CO) primary, secondary, as well as tertiary alkyl bromides and iodides can be efficiently converted into the corresponding aldehydes. Aromatic and α,β-unsaturated aldehydes can also be prepared from the parent aromatic and vinylic iodides. If the reaction is carried out in the presence of alkenes containing an electron-withdrawing substituent, the initially formed acyl radical subsequently adds to the alkene, leading to a general method for the synthesis of unsymmetrical ketones. This three-component coupling reaction can be extended successfully to allyltin-mediated reactions. Thus, β,γ-enones can be prepared from organic halides, CO, and allyltributylstannanes. In a remarkable one-pot procedure alkyl halides can be treated with a mixture of alkene, allyltributylstannane, and carbon monoxide in a four-component coupling reaction that provides β-functionalized δ,?-unsaturated ketones by the formation of three new C? C bonds. The reaction of 4-pentenyl radicals with CO leads to acyl radical cyclization, which provides a useful method for the synthesis of cyclopentanones. Certain useful one-electron oxidations can be combined efficiently with free-radical carbonylations. These findings and others discussed in this article clearly demonstrate that free-radical carbonylation can now be considered a practical alternative to transition metal mediated carbonylation.     

Alkylation and acylation of C-phosphorylated acetamidines involving CH-acidic methylene group

Reactions of sodium derivatives of C-phosphorylated acetamidines containing CH-acidic methylene group with alkyl and acyl halides were studied. The interaction occurs selectively to form the products of alkylation and acylation of methylene group, respectively. A convenient method for the synthesis of C-alkylated and C-acylated derivatives of C-phosphorylated acetamidines was developed.     

Indium-mediated mild and efficient one-pot synthesis of alkyl phenyl selenides

A mild and convenient one-pot process for synthesizing alkyl phenyl selenides is developed using indium metal. The reaction shows the selectivity for tert-alkyl, benzylic, and allylic halides over primary and secondary alkyl halides.