Photopromoted Carbonylation of Alkyl Halides Under Ambient Conditions

Photopromoted carbonylation of alkyl halides with carbon monoxide can be carried out under ambient conditions with non-precious transition metal complexes (such as cobalt complexes) catalysts. Our preliminary work showed that alkyl halides can be transformed into alkene and alkane directly under irradiation, but the esters can not be transformed. It is assumed that the carbonylation of alkyl halides may be proceeded in two ways.

STUDY ON THE CATIONIC POLYMERIZATION OF 1, 3-PENTADIENE INITIATED BY AlCl_3/ALKYL HALIDE SYSTEMS

The cationic polymerizations of 1, 3-pentadiene were initiated by AlCl_3 in n-hexaneat 30℃ in the presence of alkyl halides, i.e., tert-butyl chloride, tert-butyl bromide andisobutyl chloride. The effects of these halides on the polymer yield, molecular weight,crosslinking reaction, cyclization and polymer microstructure, have been investigated. Twomain side reactions, crosslinking and cyclization, were suppressed and reduced by theaddition of the halides. The proportion of 1, 4 units of polymer chains was increasedby the presence of the halides, which reduced the polymer yield and the molecular weightof polymers.

A NEW SYNTHESIS OF SULFONES VIA THE ZINC—ASSISTED COUPLING OF ARENESULFONYL CHLORIDE WITH ALKYL HALIDES

Arenesulfonyl chloride undergoes a facile one-pot coupling reaction with active halides assisted by zinc to give the corresponding sulfones in acceptable yields.

REGIOSELECTIVE O-ALKYLATION OF MYO-INOSITOL DERIV ATIVES WITH ALKYL HALIDES UNDER S-L PHASE TRANSFER CATALYTIC CONDITIONS

A convenient synthetic approach leading to protected inositol was described based on regioselective O-alkylation using alkyl halide under solid-liquid PTC condition

REACTIONS OF ORGANODILITHIUM COMPOUND WITH ALKYL HALIDES

The mechanism of the electron transfer reaction of 1,4-dilithio- tetraphenyl-1,3-butadiene with methyl iodide was studied.

Nickel-catalyzed umpolung C-S radical reductive cross coupling of S-(trifluoromethyl)arylsulfonothioates with alkyl halides

A new cooperative nickel reductive catalysis and N,N-dimethylformamide-mediated strategy for umpolung C–S radical reductive cross coupling of S-(trifluoromethyl)arylsulfonothioates with alkyl halides to produce alkyl aryl thioethers is described. This reaction features excellent selectivity, wide functionality tolerance, broad substrate scope, and facile late-stage modification of biologically relevant molecules.Mechanistic studies recognize initial generation of an amidyl radical anion via thermoinduced reduction of DMF with Sn, followed by umpolung reduction and single electron transfer of the nucleophilic sulfonyl moiety to form a sulphydryl radical and engage the Ni^(0)/Ni^(Ⅰ)/Ni^(Ⅲ)/Ni^(I) catalytic cycle.

C-H…X-C bonds in alkyl halides drive reverse selectivities in confined spaces

Binding of non-activated alkyl halides(2-20)in water-soluble cavitand(1)through supramolecular forces is here reported,with emphasis on the role of size and polarizability of the halogen atom in the formation of intramolecular C-H hydrogen bonds in confined spaces.Rare reverse affinity in water(RI<RBr<RCl)is surprisingly observed for the more water-soluble short alkyl halides in dynamic open-ended containers.Competitive bindings and theoretical calculations confirm the unusual selectivity and the presence of C-H hydrogen bonds in non-activated systems for the first time,pointing out the importance and effect of subtle forces on molecular recognition in confined spaces.

Immobilization of HX:[Hmim]X as Halogenating Agent, Recyclable Catalyst and Medium for Conversion of Alcohols to Alkyl Halides

HX is immobilized by reaction of halogen acid with methylimidazole, and the formed ionic liquid [Hmim]X was used as halogenating agent, catalyst as well as medium for conversion of alcohols to alkyl halides. Excellent yields were obtained. The halides produced could be easily separated from the reaction mixture via simple decantation, and the ionic liquid [Hmim]X could be regenerated conveniently by adding equivalent of halogen acids followed by removal of water.

An Efficient and Novel Synthesis of Carbamate Esters from the Coupling of Amines, Halides and Carbon Dioxide in the Presence of Basic Resin

A convenient, efficient, one-pot, novel process has been developed for the synthesis of carbamates from corresponding alkyl halides and amines using basic resin/CO2 system.

In situ Ionothermal Synthesis and Characterization of a Novel Cuprous Halide Complex

A new compound [mpba][Cu_2Br_3]（1, mpba = 4-（N-methylpyridin-4-yl）benzoic acid） has been ionothermally synthesized and characterized by single-crystal X-ray diffraction analysis, infrared spectrum, elemental analyses, fluorescence spectrum, and thermogravimetric analysis. In compound 1, the [mpba]＋ cation is a new organic template, which is obtained firstly in this work by in situ alkylation reaction of N-heterocycles 4-（pyridin-4-yl）benzoic acid with [Emim]Br（Emim = 1-ethyl-3-methyl imidazolium）. Hirshfeld surface analysis shows that weak interactions between the [mpba]＋ cations and 1D inorganic [Cu_2Br_3]~– are mainly C–H···Br hydrogen bonds. In addition, a pairwise O–H···O interaction is observed between the adjacent [mpba]＋cations. These different types of weak interactions make compound 1 stable up to 300 ℃. Fluorescence spectrum investigation shows 1 has a strong yellow emission at 555 nm. Theoretical calculation not only demonstrates compound 1 is a wild band semiconductor with a 3.3 e V band gap but also elucidates the fluorescence emission derives from the p-π＊ transition of electrons from [Cu_2Br_3]~– to [mpba]~＋.

Reductive Cleavage of the Te-Te Bond in Diphenyl Ditelluride by the Sm/CrCl_3(cat.) System: Preparation of Telluroesters and Unsymmetrical Phenyltellurides

The reduction of diphenyl ditelluride by the Sm/CrCl_3(cat.) system led to atelluride anion. This species reacted with acid chlorides, alkyl halides, and α,β-unsaturatedenoates or α,β-unsaturated ene nitriles to afford telluroesters and unsymniet-ricalphenyltellurides, respectively, in moderate to good yields under mild and neutral conditions.

Expedient copper-catalyzed borylation reactions using amino acids as ligands

Amino acids were found to be as good ligands for copper-catalyzed borylation reactions of primary and secondary alkyl halides,and the B2pin2 acted as bi-boron source for borylation.The high reaction efficiency and mild conditions make the new catalyst system a useful alternative to the recently developed methods for the preparation of alkylboronic esters.