One-pot Suzuki-Miyaura-type and Kumada-type cross-coupling reactions of 2,4-diiodo-buta-1-enes with arylboronic acids and alkyl/aryl magnesium bromides were carried out in the presence of accessibly simple catalysts under mild conditions. As a result, some 1,1,2-trisubstituted buta-1,3-dienes were obtained including the Tamoxifen-type, which have potential adjuvant therapy in women who have suf...

An iridium photocatalyst and visible light facilitate a room temperature, nickel-catalyzed coupling of (hetero)aryl bromides with activated α-heterosubstituted or benzylic C(sp3)-H bonds. Mechanistic investigations on this unprecedented transformation have uncovered the possibility of an unexpected mechanism hypothesized to involve a Ni-Br homolysis event from an excited-state nickel complex. T...

Monophosphines prepared by iron catalysed hydrophosphination have been used as pro-ligands in iron catalysed Negishi cross-coupling of alkyl bromides and diphenyl zinc reagents. The cross-coupling has been investigated with monophosphines with varying electronic properties and we find the simplest, unsubstituted phosphine to offer the optimum reaction conditions (both in terms of yield of diary...

Pivalophenone N–H imine has been found to serve as a prominent substrate for directed C–H alkylation and arylation reactions with alkyl bromides and aryl chlorides, respectively, under cobalt–N-heterocyclic carbene (NHC) catalysis. Unlike the case of the parent pivalophenone imine, the increased steric bulk of the resulting ortho-substituted pivalophenone imines allows them to undergo clean imi...

A mild and efficient nickel-catalyzed reductive cross-coupling between fluorinated secondary alkyl bromides and (hetero)aryl iodides is described. The use of FeBr2 as an additive successfully overcomes the hydrodebromination and β-fluorine elimination of fluorinated substrates and allows the efficient synthesis of a wide range of trifluoromethyl and difluoroalkyl containing aliphatic compounds ...

The application of [4+2] cycloadditions between alkenes and an N-benzoyl iminium species, generated in situ under acidic conditions, is described in the synthesis of diverse molecular scaffolds. The key reaction led to the formation of cyclic imidates in good yield and with high regioselectivity. It was demonstrated that the cyclic imidates may be readily converted into 1,3-amino alcohols. Inco...

Reaction of imidazolylidene-derived enetetramine 2 with aliphatic iodides and bromides (and with aryl iodides bearing alkene-containing side-chains in the ortho-position) leads to formation of aliphatic aldehydes through an unprecedented extrusion of a one-carbon unit from the enetetramine. An intermediate 2-alkylimidazoline 24 is proposed, where the alkyl group derives from the substrate; this...

Significance: A novel general β-arylation of protected alanine esters to yield synthetically useful (hetero)aryl alanine building blocks has been disclosed. The protocol utilizes a lithium amide to form an enolate that undergoes a palladium-catalyzed C–C coupling with various aromatic bromides. Comment: Interestingly, the reaction could be extended to α-amino acids bearing other linear alkyl ch...

Phenylhydrazines 1 substituted with two or three long-chain alkyl, alkoxy or alkylsulfanyl groups were successfully prepared by acid-induced removal of the Boc group in hydrazides 2. The reaction is carried out with 5 equivalents of TfOH in CF(3)CH(2)OH/CH(2)Cl(2) at -40 °C for 1.5 min. Under these conditions, the deprotected hydrazine 1 is fully protonated, which increases its stability in the...

We are reporting the unexpected reaction between bromo-boron subphthalocyanine (Br-BsubPc) and THF, 1,4-dioxane or γ-butyrolactone that results in the ring opening of the solvent and its addition into the BsubPc moiety. Under heating, the endocyclic C-O bond of the solvent is cleaved and the corresponding bromoalkoxy-BsubPc derivative is obtained. These novel alkoxy-BsubPc derivatives have rema...