The catalytic asymmetric conjugate addition to α , β -unsaturated compounds is one of the most powerful carbon -carbon and carbon -heteroatom bond -forming reactions in organic synthesis. The reaction is enormously useful for the construction of enantioenriched, highly functionalized carbon skeletons for the total syntheses of numerous biologically active compounds. The scope of the reaction is broad, owing to the availability of a large variety of donor and acceptor compounds. The high potential of this synthetic method is evident with the possibility of building multiple stereocenters in a single synthetic operation, and many asymmetric catalytic systems can exhibit high reactivity and stereoselectivity. In this chapter, recent advances in catalytic asymmetric conjugate addition reactions are described according to four categories: (i) conjugate addition of organometallics, (ii) conjugate addition of other carbon -centered nucleophiles, (iii) tandem conjugate addition reactions, and (iv) conjugate addition of heteroatom nucleophiles. 8A.2. CATALYTIC ASYMMETRIC CONJUGATE ADDITION OF ORGANOMETALLICSThe catalytic asymmetric conjugate addition of organometallic reagents to electrophilically activated olefi ns constitutes one of the most powerful methods for carbon -carbon Catalytic Asymmetric Synthesis, Third Edition, Edited by Iwao Ojima

Optically active tertiary aminonaphthol ligands were obtained by a new, convenient procedure and were found to catalyze the enantioselective alkenyl and phenyl transfer to aldehydes in high yields and excellent enantiomeric excesses (ee's). The catalytic asymmetric introduction of alkynyl functionality to α-amino acid derivatives was realized by the direct addition of terminal alkynes to α-imino ester in the presence of chiral copper(I) complex under mild reaction conditions.

The title compound, C36H28O4P2·CH4O, was synthesized directly from the methoxy analogue. The crystal structure shows that one OH group interacts with an O atom of a phosphine oxide group in an adjacent mol­ecule, while the other OH group complexes with the methanol solvent molecule via intermolecular hydrogen bonds. An O atom of one phosphine oxide group interacts with the hydroxy H atom of methanol via a hydrogen bond. There are intra‐ and intermolecular π–π interactions between the phenyl rings. All these interactions result in the formation of supramolecular chiral parallelogram channels via self‐assembly.