This report describes a number of new synthetic approaches towards methyl-substituted mono- and diepoxy alcohols that serve as substrates for endo-selective epoxide-opening cascades. The key transformations involve the manipulation of alkynes. Highlighted are the directed methylmetalation of bishomopropargylic alcohols, the bromoallylation of alkynes, and Pd-catalyzed cross-coupling between an ...

O-Vinyl oximes were synthesised from the reaction of oximes with activated alkynes and subsequently rearranged using gold catalysis to afford highly substituted pyrroles in an efficient and regiocontrolled process. Additionally, pyrroles were formed directly from oximes and activated alkynes in a multifaceted catalysis process.

A rhodium-catalyzed intermolecular hydroarylation of internal alkynes with N-1-phenylbenzotriazoles via C-H bond activation is described. This transformation offers an alternative method for the hydroarylation of internal alkynes with high stereoselectivity. The reaction mechanism was discussed according to the deuterium-labeling experiments.

A convenient method for the preparation of alkynes and alkynyl esters from ketones and β-keto esters is described which involves the formation of vinyl triflates, followed by elimination with tetrabutylammonium fluoride trihydrate, to give alkynes. Unlike established elimination methods, the method requires neither a strong base nor anhydrous conditions.

We systematically examined the effect of different esters on the rhodium-catalyzed intermolecular [5+2] cycloaddition of 3-acyloxy-1,4-enynes and alkynes with a concomitant 1,2-acyloxy migration. Significant rate acceleration was observed for benzoate substrates bearing an electron-donating substituent. The cycloaddition can now be conducted under much more practical conditions for most termina...

We have developed efficient copper-catalyzed additions of P(O)H compounds to alkynes, and the reactions provided the regio- and stereoselective E-alkenylphosphine oxides under catalysis of the commercially available and inexpensive copper catalyst system CuI/ethylenediamine. This finding is the first example of copper-catalyzed hydrophosphinylation of alkynes to synthesize alkenylphosphine oxides.

We have developed a nickel-catalyzed transformation, in which phthalimides react with trimethylsilyl-substituted alkynes in the presence of Ni(0)/PMe3/MAD catalyst to provide isoindolinones. The reaction process displays an unusual mechanistic feature-decarbonylation and alkylidenation. The use of both trimethylsilyl-substiuted alkynes and MAD was found to be essential for the transformation wi...

A regioselective synthesis of substituted pyrroloquinolinones via a ruthenium-catalyzed oxidative cyclization of substituted N-carbamoyl indolines with alkynes is described. The cyclization reaction was compatible with various symmetrical and unsymmetrical alkynes including substituted propiolates. Later, we performed the aromatization of pyrroloquinolinones into indole derivatives in the prese...

A simple protocol for iron-catalyzed cross-coupling of nonactivated secondary alkyl bromides and iodides with alkynyl Grignard reagents at room temperature has been developed. A wide range of secondary alkyl halides and terminal alkynes are tolerated to afford the substituted alkynes in good yields. A slight modification of the reaction protocol also allows for cross-coupling with a variety of ...

The Cu(I)-catalyzed denitrogenative transannulation reaction of pyridotriazoles with terminal alkynes en route to indolizines was developed. Compared to the previously reported Rh-catalyzed transannulation reaction, this Cu-catalyzed method features aerobic conditions and much broader scope of pyridotriazoles and alkynes.