Precision Deuteration Using Cu-Catalyzed Transfer Hydrodeuteration to Access Small Molecules Deuterated at the Benzylic Position.

A highly regio- and chemoselective Cu-catalyzed aryl alkyne transfer hydrodeuteration to access a diverse scope of aryl alkanes precisely deuterated at the benzylic position is described. The reaction benefits from a high degree of regiocontrol in the alkyne hydrocupration step, leading to the highest selectivities reported to date for an alkyne transfer hydrodeuteration reaction. Only trace isotopic impurities are formed under this protocol, and analysis of an isolated product by molecular rotational resonance spectroscopy confirms that high isotopic purity products can be generated from readily accessible aryl alkyne substrates.

Regio- and Stereoselective Electrophilic Cyclization Approach for the Protecting-Group-Free Synthesis of Alkaloids Lennoxamine, Chilenine, Fumaridine, 8-Oxypseudoplamatine, and 2- O-(Methyloxy)fagaronine.

A unified strategy for protecting-group-free synthesis of alkaloids lennoxamine, chilenine, fumaridine, 8-oxypseudoplamatine, and 2- O-(methyloxy)fagaronine is reported. The core isoindolin-1-one and isoquinolin-1-one structures were built by a silver-catalyzed regio- and stereoselective cyclization of methyl 2-alkynylbenzimidates. The regioselectivity of cyclization was achieved by utilizing the intrinsic functionality of alkaloids.