α‐Addition of 1,3‐Dicarbonyl Compounds to Acetylenic Ketones Catalyzed by Triphenylphosphine

The present work describes a simple way of synthesizing multifunctional compounds by α‐addition of 1,3‐dicarbonyl compounds to acetylenic ketones catalyzed by triphenylphosphine in moderate to good yields.     

Substitution of Acyl for Acetyl with N‐Acylbenzotriazoles Catalyzed by Samarium Triiodide

Catalyzed by samarium triiodide (SmI₃), substitution of acyl with N‐acylbenzotriazoles for acetyl in acetoacetic esters and acetylacetone proceeds smoothly under neutral conditions in open air, affording the corresponding β‐keto esters and β‐diketones in good yields.     

Synthesis of 5‐Cyano‐1,3‐dioxoalkanes by Reaction of 1,3‐Dicarbonyl Dianions with Bromoacetonitrile

5‐Cyano‐1,3‐dioxoalkanes were prepared by reaction of 1,3‐dicarbonyl dianions with bromoacetonitrile.     

Mannich‐Type Reaction Catalyzed by Silica‐Supported Fluoroboric Acid under Solvent‐Free Conditions

Three‐component Mannich‐type reaction of aldehydes, aromatic amines, and silyl enolate proceeded smoothly to afford β‐amino carbonyl compounds with good yields in the presence of a catalytic amount of HBF₄‐SiO₂.     

Isocyanide‐Catalyzed Reaction of Tetracyanoethylene and Activated 1,3‐Dicarbonyl CH‐Acid Compounds: A Rapid and Efficient Synthesis of Pyran Annulated Heterocyclic Systems

An isocyanide‐catalyzed reaction between tetracyanoethylene and various activated CH‐acid compounds to afford the corresponding pyran annulated heterocyclic ring systems, in high yield at room temperature within a few minutes, is described. To the best of our knowledge, this is the first example in which isocyanide functions as only a catalyst but not a reagent.     

Iodine‐Catalyzed Conversion of β‐Dicarbonyl Compounds into β‐Enaminones Within a Minute Under Solvent‐Free Conditions

Synthesis of β‐enaminones from β‐dicarbonyl compounds has been achieved in high yields within a minute using primary and aromatic amines and catalytic amounts of iodine under solvent‐free conditions at room temperature.     

α‐Bromination of 1,3‐Dicarbonyl Compounds Using Dess–Martin Periodinane (DMP) and Tetraethylammonium Bromide (TEAB)

A mild and expeditious method for α‐bromination of 1,3‐dicarbonyl compounds using Dess–Martin periodinane and tetraethylammonium bromide is described.     

Free Radical Cyclization of 1,3‐Dicarbonyl Compounds Mediated by Manganese(III) Acetate with Alkynes and Synthesis of Tetrahydrobenzofurans,Naphthalene, and Trifluoroacetyl Substituted Aromatic Compounds

Furan derivatives were obtained from radical cyclizations of 1,3‐dicarbonyl compounds mediated by Mn(OAc)₃ with phenyl acetylene 2a (14–66% yields). Naphthalene derivates 4a and 4b were produced in the treatments with 2a. In addition to these, trifluoroacetyl substituted naphthalene 4c, benzofuran 4d, and benzothien 4e were obtained in the reactions of trifluoromethyl‐1,3‐dicarbonyls (1 g–i) with 2a.     

Formation of α,α''''-Bis(substituted benzylidene)cycloalkanones from Masked Aldehydes Promoted by Samarium(III) Triiodide

~~Formation of α,α'-Bis(substituted benzylidene)cycloalkanones from Masked Aldehydes Promoted by Samarium(III) Triiodide~~     

Facile and Efficient Synthesis of Substituted 1,4‐Dithiafulvalenes from β‐Dicarbonyl Compounds

A facile and efficient synthetic route to substituted 1,4‐dithiafulvalenes has been developed. The precursors 2 may be easily prepared from the reactions of β‐dicarbonyl compounds 1 with CS₂ and 1,2,3‐tribromopropane under mild conditions. The elimination of HBr of 2 in basic media furnishes corresponding acetyl substituted 1,4‐dithiafulvalenes 3 in 85–93% yields. The aldol condensation reaction of 2 with various arylaldehydes affords alkenoyl substituted 1,4‐dithiofulvalenes 4 in high to excellent yields.     

Formation of a,a＇-Bis（substituted benzylidene）cycloalkanones from Masked Aldehydes Promoted by Samarium（III） Triiodide

1,1-Diacetates 1 and N-[(1-benzotriazol-l-yl)alkyl]amides 2, both masked forms of aldehydes, could undergo deprotection and condensation with cycloalkanones in a one-pot procedure promoted by samarium(Ⅲ) iodide (SmI3) to afford a,a‘-bis(substituted benzylidene)cycloalkanones in good yields.     

Unusual p‐Toluene Sulfonic Acid–Catalyzed Carbon–Carbon Bond Formation

Abstract

Attempts to synthesize the antidepressant drug atomoxetine directly by p-TSA‐catalyzed reaction between o‐cresol and N‐methyl‐3‐phenyl‐3‐hydroxypropyl amine in toluene at reflux temperature surprisingly resulted in the formation of ortho‐substituted phenol derivative. The structure is unambiguously confirmed by single crystal X-ray.     

Catalytic Thioalkylation of Phenols Based on Mannich‐Type Phenol

A thioalkylation of phenols involving reactive phenols, aldehydes, and thiols is described under Mannich‐type phenol catalysis to afford thiomethyl phenols in good yields.     

β-Diketone Synthesis by Reaction of α-Haloketones with Acid Chlorides or Acid Anhydrides Promoted by Samarium Triiodide

Promoted by SmI₃, α-haloketones were reacted with acid chlorides or acid anhydrides and β-diketones were synthesized via intermediate samarium enolates.     

Novel Carbon–Carbon Bond Formation between N‐Methyl‐3‐phenyl‐3‐hydroxypropylamine and Cresols Catalyzed by p‐Toluenesulphonic Acid

The p‐toluenesulphonic acid–catalyzed reaction between appropriate cresols and N‐methyl‐3‐phenyl‐3‐hydroxypropylamine in refluxing toluene resulted in the formation of o‐substituted phenol derivatives by an aromatic nucleophilic substitution reaction.     

Carbon–Carbon Bond Formation by Radical Cyclization: Regioselective Synthesis of Spiro Heterocyclic Compounds by n Bu3SnH‐Mediated Reaction

Several spiro heterocyclic compounds have been regioselectively synthesized in excellent yield by ⁿ Bu₃SnH‐AIBN‐mediated radical cyclization of 4‐(2′‐bromoaryloxymethyl)‐1‐methylquinolin‐2(1H)‐ones in refluxing benzene under nitrogen for 4 h.     

Microwave‐Assisted Selenium Dioxide Oxidation of Camphor Derivatives to α‐Dicarbonyl Compounds and Oxoimines

Camphor‐derived α‐dicarbonyl compounds and 3‐oxo‐camphorsulfonylimine have been synthesized from the corresponding ketones or sulfonylimine by microwave‐assisted oxidation with selenium dioxide. Compared to the classical reaction conditions, good yields were obtained in much shorter reaction times. Additionally, the selenium precipitation is more quantitative, and its removal from the reaction mixture is easier.     

Synthesis of 1,3-Diketones by Reaction of α-Haloketones with Acyl Cyanides Promoted by Samarium Diiodide

α-Haloketones reacted with acyl cyanides to form 1,3-diketones in the presence of samarium diiodide. The reaction was assumed to proceed via a mechanism involving samarium enolates formed in situ from α-haloketones.     

Efficient Synthesis of 1,5‐Benzodiazepine Derivatives by Ytterbium Trichloride–Catalyzed Condensation of o‐Phenylenediamine and Ketones

1,5‐Benzodiazepines are synthesized in good to excellent yields by ytterbium trichloride (YbCl₃)–catalyzed condensation of o‐phenylenediamine and ketones under mild and solvent‐free conditions. The Lewis acid–type catalyst, ytterbium trichloride, is found to be water stable and reusable.     

Gallium Triiodide–Catalyzed Organic Reaction: A Convenient Procedure for the Synthesis of Coumarins

Abstract

Gallium triiodide, which was generated in situ by the reaction of gallium metal and iodine, was used as an efficient catalyst in the Pechmann condensation of phenols with ethyl acetoacetate, leading to the formation of coumarins. The reaction proceeded in dichloromethane at room temperature with good to excellent yields.