Chiral bicyclo[3.3.0]octadienes carrying two alkoxy- or alkynyloxy side chains are highly valuable ligands for asymmetric catalysis but have never been explored regarding their liquid crystalline self-assembly. Therefore, a series of was synthesised and studied by differential scanning calorimetry (DSC), polarising optical microscopy (POM) X-ray diffraction (XRD) to understand the role terminal...

The Au(I)-catalyzed reactions of (2-alkynyl)phenylsulfonyl azetidines bearing terminal and non-terminal alkynes in the presence methanol as protic nucleophile to form benzosultams derivatives were studied by density functional theory (DFT) calculations. Our study highlights that gold(I) catalyzed nucleophilic addition nitrogen on alkyne is favored over direct ring opening azetidine methanol, co...

The importance of cyclopentanoid natural products continues to inspire the development of methods for the synthesis of 5-membered rings. For example, the Conia–ene reaction provides an atomeconomical synthesis of methylenecyclopentanes by the thermal cyclization of e-acetylenic carbonyl compounds. While the classic thermal reaction is limited to the exocyclic cyclization mode, group 6 metal com...

Stereodefined enol derivatives of aldehydes are prepared from terminal alkynes. Specifically, terminal alkynes are known to undergo Cp2ZrCl2-catalyzed methylalumination. Here, we show that the resultant vinylalanes can be oxygenated with peroxyzinc species to generate trisubstituted enolates. Electrophilic trapping with carboxylic anydrides or silyl triflates yields trisubstituted enol esters o...

The scope of the Cu(I)-catalyzed [2 + 3] azide/alkyne cycloaddition (CuAAC, click chemistry) as a key reaction for the conjugation of ferrocene derivatives to N-terminal functionalized PNA oligomers is explored herein (PNA: peptide nucleic acid). The facile solid-phase synthesis of N-terminal azide or alkyne-functionalized PNA oligomer precursors and their cycloaddition with azidoferrocene, eth...

Density functional theory calculations demonstrate that the reversal of regiochemical outcome of the addition for substituted methyl propiolates in the rhodium-catalyzed [(2 + 2) + 2] carbocyclization with PPh3 and (S)-xyl-binap as ligands is both electronically and sterically controlled. For example, the ester functionality polarizes the alkyne π* orbital to favor overlap of the methyl-substit...

Historically used in stoichiometric hydroalumination chemistry, recent advances have transformed aluminium hydrides into versatile catalysts for the hydroboration of unsaturated multiple bonds. This catalytic ability is founded on defining reactivity with alkynes and alkenes: 1,2-hydroalumination π-system. manuscript reports hydride catalyzed dehydroborylation terminal alkynes. A tethered intra...

This review discusses the emergence of alkyne metathesis as a valuable synthetic tool applicable in the synthesis of complex molecules and polymer science.

We synthesized the first multifunctionalized phosphoinositide polyphosphate derivatives featuring a photo-removable protecting group (“cage”), photo-crosslinkable diazirine group, and terminal alkyne useful for click chemistry. demonstrate that lipid readily enter cells. After photo-crosslinking, cell fixation fluorescent tagging via chemistry, we determined intracellular location of before aft...