The direct electrophilic, nucleophilic, and amphiphilic allylations of allylic alcohol by use a palladium catalyst organometallic reagents such as organoborane organozinc has been developed. phosphine–borane compound works the effective ligand for palladium-catalyzed amination alcohol. Thus, with secondary amines, reaction was completed in only 1 h, even at room temperature.

Abstract The Mizoroki‐Heck reaction is one of the most valuable reactions for functionalizing C−C double bonds in presence a Pd catalyst. This protocol suitable C(sp 2 )‐halide with terminal olefin to produce trans‐1,2‐disubstituted olefin. However, reports internal olefins are rare and impractical due low reactivity problems product diastereoselectivity. In this review, we summarize aryl or alkyl halides illustrate their reactivities stereoselectivities.

The abilities of dipyrrolyldiketone boron complexes as hydrogen-bonding donor organocatalysts were examined by the Mannich-type reaction N-acyl heteroarenium chlorides with 1-methoxy-2-methyl-1-trimethylsiloxy-1-propene, well classical N-alkylation amines trityl chloride under base-free conditions. 1H NMR examinations interaction between pyrrole NH catalyst and Cl– in salt suggested that activation occurs through anion binding catalyst.

A light-driven atom-transfer radical substitution (ATRS) and carboesterification reaction of alkenes with alkyl halides has been developed using PTH as the organo-photoredox catalyst. Two types products were obtained, depending on additive solvent used during reaction. Primary, secondary, tertiary reacted to give ATRS products. This protocol several advantages: it requires mild conditions a low catalyst loading exhibits broad substrate scope good functional group tolerance. Mechanistic...

In this paper, we report efficient cyanation of various peptides containing the α-bromocarbonyl moiety using a Cu-catalyzed radical-based methodology employing zinc cyanide as source. Mechanistic studies revealed that in situ formed CuCN was key intermediate during catalytic cycle. Our method could be useful for synthesis modified quaternary carbons.

Abstract Nucleophilic substitutions, including S N 1 and 2, are classical reliable reactions, but a serious drawback is their intolerance for both bulky nucleophiles chiral tertiary alkyl electrophiles the synthesis of quaternary carbon center. An RN reaction via radical species another conventional method used to carry out substitution reactions halides, cannot be used. Therefore, stereospecific nucleophilic using has not yet been well studied. In this paper, we describe alcohols non‐chiral...

Abstract Herein, we report an efficient method for the tertiary alkylation of a ketone by using α‐bromocarbonyl compound as alkyl source in combined Cu‐organocatalyst system. This dual catalyst system enables addition radical to enamine. Mechanistic studies revealed that catalytically generated enamine is key intermediate catalytic cycle. The developed can be used synthesize substituted 1,4‐dicarbonyl compounds containing quaternary carbons bearing various chains.

The combination of Pd catalyst and diethylzinc with triethylborane promotes the amphiphilic allylation aldimines 2,3-bismethylenebutane-1,4-diol derivatives to serve as bis-allylic zwitterion species form 3,4-bismethylenepiperidines via a formal [4 + 2] cycloaddition reaction. 3,4-Bismethylenepiperidine rings are applicable for synthesis isoquinoline Diels-Alder reaction followed by an oxidation DDQ.

A palladium-catalyzed nucleophilic allylation of aldehydes with vinylcyclopropane in the presence diethylzinc proceeded to provide homoallyl alcohols <i>anti</i> stereoselectivity. Aldimines prepared from aldehyde and primary amines situ underwent a similar give homoallylamines <i>syn</i> The resulting could be converted by treatment tetranuclear zinc cluster into γ-vinyl-δ-valerolactones γ-vinyl-δ-valerolactams, respectively.

Abstract A variety of π‐electronic ion‐pairing assemblies can be constructed by combining anion complexes systems and countercations. In this study, a series anion‐responsive molecules, dipyrrolyldiketone Pt II containing phenylpyridine ligand, were synthesized. The resulting exhibited phosphorescence emission, with higher emission quantum yields (0.30–0.42) microsecond‐order lifetimes, solution‐state binding, as revealed our spectroscopic analyses. These displayed solid‐state assemblies,...

Abstract The C−C bond formation between active methylene compounds and allylic alcohols has been newly developed by using a palladium complex as catalyst together with phosphine‐borane ligand. best ligand for this direct allylation revealed to be Ph 2 P(CH ) 4 (9‐BBN) produce variety of desirable allylated products in high yields. magnified image

Heteroleptic PtII complexes comprising π-extended dipyrrins and 2-phenylquinoline were prepared. Single-crystal X-ray analysis disclosed the stepped conformations of two ligand moieties in these complexes. The enantiomers could be separated by HPLC their configurations determined from CD spectroscopy results TD-DFT calculations. Transient absorption measurements revealed excited-state dynamics characterized fast intersystem crossing microsecond-order triplet-state lifetimes.

Abstract Nucleophilic substitutions, including S N 1 and 2, are classical reliable reactions, but a serious drawback is their intolerance for both bulky nucleophiles chiral tertiary alkyl electrophiles the synthesis of quaternary carbon center. An RN reaction via radical species another conventional method used to carry out substitution reactions halides, cannot be used. Therefore, stereospecific nucleophilic using has not yet been well studied. In this paper, we describe alcohols non‐chiral...

A terminal alkyne is one of the most useful reactants for synthesis and alkene derivatives. Because an undergoes addition reaction at a C–C triple bond or cross-coupling C–H bond. Combining those patterns could realize new methodology to synthesize complex molecules including multiple bonds. In this report, we found that 3 equivalents 1 (aryl substituted alkyne) α-bromocarbonyl compound 2 (tertiary alkyl radical precursor) tandem addition/Sonogashira coupling produce 1,3-enyne possessing...

Abstract Herein, we report an efficient method for the tertiary alkylation of a ketone by using α‐bromocarbonyl compound as alkyl source in combined Cu‐organocatalyst system. This dual catalyst system enables addition radical to enamine. Mechanistic studies revealed that catalytically generated enamine is key intermediate catalytic cycle. The developed can be used synthesize substituted 1,4‐dicarbonyl compounds containing quaternary carbons bearing various chains.

In this study, we discovered that α-bromocarboxamides react with alkynols containing tertiary alcohol moieties to produce congested ethers or heterocycles. Here, the etherification and hydroamidation reactions can be controlled by a suitable base. Both C-O C-N bond formations occurred without transition-metal catalyst. The stereospecific cyclization of diastereo-enriched α-bromocarboxamide afforded corresponding ether heterocyclic compound.

Abstract Indoles are one of the most valuable nucleophiles in Michael additions catalyzed by a proper Lewis acid. In this paper, we found that cationic iron salt is effective to carry out addition indoles. β-Mono- and disubstituted enones reacted smoothly with indoles under our conditions. The catalyst very active, maximum TON was up 425. Moreover, iron-catalyzed conditions enabled chemoselective substrate possessing both enone α,β-unsaturated ester moieties.

Abstract The title reaction is promoted by diethylzinc.