The rhodium-catalyzed asymmetric addition reaction of organoboron reagents to a,ß-unsaturated compounds has seen significant growth in the past two decades for their user-friendly reaction conditions, which generally allow the use of water as a cosolvent. This chapter highlights advancements ranging from 2004 to 2017 in this field and organizes the content in terms of the applicable substrates with respect to the chiral ligands. Bis-sulfoxide ligands emerged as one of the privileged ligand family in C-H oxidation reaction by coordinating Pd with sulfur atoms. Ligands with two distinct chelating centers are regarded as hybrid ligands. While dienes generally display greater catalytic activity than phosphorus ligands, the coordinating ability of diene ligands is weaker than that of phosphine-based ones. a,ß-unsaturated esters are generally good reaction partners in the Rh-catalyzed conjugate addition reactions for 1,4-addition products. Nitroolefin compounds are excellent substrates in the rhodium-catalyzed asymmetric conjugate addition reactions as a result of their highly electrophilic nature.
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