A unique rhodium(I)-catalyzed asymmetric B-H insertion of α-diazo carbonyl compounds with easily available amine-borane adducts was achieved using a newly developed C1-symmetric chiral diene as ligand. This first Rh(I)-carbene-directed B-H insertion example represents an attractive and promising approach for synthesis of highly enantioenriched organoboron compounds, allowing for the efficient construction of α-boryl esters and ketones with excellent enantioselectivities (up to 99% ee) under exceptionally mild conditions.

The design and development of a novel class of chiral sulfur-olefin hybrid ligands with high synthetic feasibility are described. These new sulfoxide-olefin ligands showed excellent catalytic activities and enantioselectivities (up to 98% ee) in rhodium-catalyzed asymmetric 1,4-addition reactions of aryl boronic acids to α,β-unsaturated carbonyl compounds.

Indole 2,5-diketopiperazines (DKPs) are an important type of metabolic cyclic dipeptides containing a tryptophan (Trp) unit possessing a range of interesting biological activities. The intriguing structural features and divergent activities...