Synthesis of Chiral Biphenyl Monophosphines as Ligands in Enantioselective Suzuki-Miyaura Coupling.

Herein, we describe our design and synthesis of novel chiral monophosphine ligands by the short-step addition of chiral lactates as side chains to the well-known ligand SPhos/RuPhos. The new chiral ligands were shown to be highly efficient in palladium-catalyzed Suzuki-Miyaura coupling, providing a series of axially chiral biphenyl products in high yield and high enantioselectivity. Furthermore, the gram-scale reaction and the diverse conversions of the products demonstrated the potential utility of the approach.

Intramolecular Imino-ene Reaction of Azirines: Regioselectivity, Diastereoselectivity, and Computational Insights.

Intramolecular imino-ene reaction of 2 H-aziridine has been studied experimentally and computationally, demonstrating that (1) the concerted process takes place regioselectively on the alkene E-CH group; (2) the geometry of the N-linker impacts the reaction activation energy and diastereoselectivity significantly, with pyramidal alkyl amine as the linkage, an exclusive cis-product is achieved; (3) when the reaction has to occur with the Z-CH group, the cis-diastereoselectivity is solely observed regardless of the nature of the N-linkage.

Stereoselective synthesis of all-cis boryl tetrahydroquinolines via copper-catalyzed regioselective addition/cyclization of o-aldiminyl cinnamate with BPin.

A copper catalyzed intramolecular 1,2-carboboration of o-aldiminyl cinnamate has been realized in both regio- and stereoselective fashions. This reaction provides a convenient entry to highly valuable and otherwise challenging cis-2,3,4-trisubstituted tetrahydroquinolines carrying a 4-boryl group. An unusual non-Michael addition intermediate or alternatively, a cyclic enolate is proposed to account for the intriguing all-cis configuration in the final products.