Exploring the versatility of the Johnson-Claisen rearrangement: access to functionally versatile δ-ethoxycarbonyl-α,β-unsaturated nitriles

A practical entry into δ-ethoxycarbonyl-α,β-unsaturated nitriles is described. α,β-Unsaturated aldehydes were converted to cyanohydrins, by employing either KCN in aqueous acid, or by using TMSCN with catalytic K₂CO₃, followed by acid hydrolysis of the TMS ether. These cyanohydrins underwent a Claisen rearrangement employing a modified Johnson-Claisen protocol to yield unsaturated nitriles in good yields and with moderate E/Z selectivity.     

Highly enantioselective copper-catalyzed allylic alkylation with atropos phosphoramidites bearing a D2-symmetric biphenyl backbone

A novel class of atropos dibridged biphenyl phosphoramidites bearing a D₂-symmetric biphenyl backbone was prepared and applied as chiral ligands in the copper-catalyzed allylic alkylation with Grignard reagent. The alkylation products were obtained in quantitative yields with high regioselectivities up to 94:6 of S_N2′/S_N2 ratio and enantiomeric excesses up to 91.1% for S_N2′ products. The unique D₂-symmetric backbone ligands have the advantages of easy preparation and sufficient reusability of their key intermediates from the undesired isomers.     

HBF4·OEt2 as a mild and versatile reagent for the Ritter amidation of olefins: a facile synthesis of secondary amides

A variety of alkenes undergo smooth amidation with nitriles in the presence of HBF₄·OEt₂ at room temperature under mild conditions to afford the corresponding secondary amides in good to excellent yields. This is a highly efficient method for the preparation of α-aryl ethyl amides especially from vinyl arenes without any side reactions such as olefin polymerization. The use of readily available and easy to handle reagent HBF₄·OEt₂ makes this method simple, convenient, and practical.     

Selectfluor-promoted fluorination of piperidinyl olefins

A simple and straightforward synthesis of 1-substituted-4-aryl-5-fluoro-1,2,3,6-tetrahydropyridine (3) or 1-substituted 4-diarylmethanoyl-4-fluoropiperidine (6) by the treatment of piperidinyl exo- or endo-olefin with 1-chloromethyl-4-fluoro-1,4-diazoniabicyclo[2.2.2]octane bis(tetrafluoroborate (Selectfluor) is reported. Two transformations from endo-olefin 1 to allylic fluoride 3 and from exo-olefin 2 to fluorohydrin 6 proceed via allylic fluorination and fluorohydroxylation in moderate yields. It presents two novel reactions promoted by Selectfluor and broadens the scope of application.     

Cross-coupling of homoallylic alcohols with styrene

A cross-coupling reaction between a homoallylic alcohol and styrene is described to broaden the scope of the titanium alkoxide tether-mediated coupling reactions. Particularly noteworthy is exceptional 1,3-diastereoselectivity by o-vinylanisole in coupling with a Z-homoallylic alcohol.     

磺酸型树脂酰胺化修饰及修饰产物的吸附脱硫研究

吸附技术以其低成本、低损耗和非破坏性等特征,在化工的清洁化方面受到广泛关注,对于汽油、柴油等烃类燃料的深度脱硫而言,吸附工艺正逐步显示出良好的应用前景[1～3].吸附剂是吸附技术的核心,已经使用或正在研制的烃类脱硫用吸附剂主要是一些无机材料,如经过不同修饰的分子筛和金属氧化物等[4～6].有机高分子吸附剂的开发研究还处于起步阶段,但已经发现有些聚合物材料可以通过化学修饰或负载,起到对烃体系中硫化物的吸附脱除作用[7～9].     

Direct Electrochemical Ritter-Type Amination of Electron-Deficient Arenes

Due to the high oxidation potentials of electron-deficient aromatic hydrocarbons, it is difficult to achieve the direct oxidative C(sp²)−H bonds functionalizations of such substrates. Herein, we develop a Ritter-type amination of electron-deficient aromatics by merging electricity and sulfate. This practical and straightforward method provides a series of acetanilides from simple electron-deficient arenes, including mono-, di- and tri-substituted arenes (22 examples, up to 75 %) with moderate to good yields under mild conditions. This method is characterized by cheap and readily available regents, atom and step economy.     

I2-Mediated Oxidative Amidation of Aryl Methyl Ketones: Synthesis of Primary α-Ketoamides Using Ammonium Carbamodithioate as Amine Surrogate

Here we report the preparation of primary α-ketoamides via a highly efficient molecular iodine-mediated oxidative amidation of aryl methyl ketones with ammonium carbamodithioate. A self-sequenced iodination/nucleophilic substitution/Kornblum oxidation/amidation mechanism was proposed. In this mechanism, α-thiocyanatoacetophenone is the key intermediate.     

2-Amino-4-(aminomethyl)thiazole-based derivatives as potential antitumor agents: design,synthesis, cytotoxicity and apoptosis inducing activities

Novel 2-amino-4-(aminomethyl)thiazole derivatives were designed and synthesized by a facile method including the Hantzsch construction of thiazole core followed by amidation and nucleophilic substitution steps. Bioassay results showed that 4-(tert-butyl)-N-[4-(piperazin-1-ylmethyl)thiazol-2-yl]-benzamide and 4-(tert-butyl)-N-{4-[(4-piperidinopiperidin-1-yl)methyl]thiazol-2-yl}benzamide possessed similar activities compared with 5-fluorouracil. The 4-piperidino-piperidin-1-yl-containing derivative also suppressed proliferation of cultured tumor cells by inducing apoptosis.