Highly enantioselective copper-catalyzed propargylic substitution of propargylic acetates with 1,3-dicarbonyl compounds.

Enantioselective Cu-catalyzed decarboxylative propargylic amination of propargyl carbamates

A copper-catalyzed asymmetric propargylic amination with a chiral ketimine P,N,N-ligand that proceeds via decarboxylation of propargyl carbamates has been developed. The reaction can be performed under the mild condition for a broad range of substrates, providing the corresponding propargylic amines in high yields and with up to 97% ee. This reaction represents a new and facile access to optica...

Copper-catalyzed propargylic substitution of dichloro substrates: enantioselective synthesis of trisubstituted allenes and formation of propargylic quaternary stereogenic centers.

An easy and versatile Cu-catalyzed propargylic substitution process is presented. Using easily prepared prochiral dichloro substrates, readily available Grignard reagents together with catalytic amount of copper salt and chiral ligand, we accessed a range of synthetically interesting trisubstituted chloroallenes. Substrate scope and nucleophile scope are broad, providing generally high enantios...

Highly Enantioselective Catalytic Vinylogous Propargylation of Coumarins Yields a Class of Autophagy Inhibitors.

A highly enantioselective copper-catalyzed vinylogous propargylic substitution has been developed. Aromatic and aliphatic propargylic esters react smoothly with substituted coumarins under mild reaction conditions to give the desired products with excellent yields and enantioselectivities. Subsequent single-step transformations enable the synthesis of a wide range of multifunctional and diverse...

Highly diastereo- and enantioselective copper-catalyzed propargylic alkylation of acyclic ketone enamines for the construction of two vicinal stereocenters.

The first highly diastereo- and enantioselective propargylic alkylation of acyclic ketone enamines to form vicinal tertiary stereocenters has been reported by employing copper catalysis in combination with a bulky and structurally rigid tridentate ketimine P,N,N-ligand.

Enantioselective propargylic [1,3]-rearrangements: copper-catalyzed O-to-N migrations toward C–N bond formation† †Electronic supplementary information (ESI) available. See DOI: 10.1039/c7sc01042g Click here for additional data file. Click here for additional data file.