Palladium‐Catalyzed Asymmetric Conjugate Addition of Aryl–Metal Species

Abstract

The objective of this review is to summarize developments in the recently discovered area of palladium‐catalyzed asymmetric Michael additions of organometallic reagents to activated electron‐deficient olefins in its practical and theoretical aspects. The methodology has been rapidly developed in the last five years as a useful alternative approach to complement the already existing copper‐ and rhodium‐catalyzed variants, especially in the area of asymmetric aryl transfer to typical Michael acceptors. Although very difficult to control because of numerous side reactions, this palladium catalysis is very promising for applications both in academia and in industry. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)

Rhodium‐ and Palladium‐Catalyzed Asymmetric Conjugate Additions

“…1) Such high, and fluctuating, prices hampers the use of Rh-catalyzed ECA on a large industrial scale, and creates a need for alternative methodologies based on cheaper transition metals, such as palladium. Several reviews have been produced on the subject of Pd-catalyzed ECAs [15,[230][231][232][233][234].…”

Desulfitative Pd-catalysed coupling reaction using benzenesulfonyl chlorides and enones as the coupling partners

“…Cacchi and more recently de Vries and Minnaard reported conditions allowing such conjugate addition using aryl halides as the coupling partners (Scheme 1, middle). 4,5 The palladium-catalysed desulfitative conjugate addition of phenylazo sulfones, 6a sodium sulfinates 6b or arylsulfonyl hydrazides 6c with α,β-unsaturated carbonyl compounds has also been described (Scheme 1, bottom). On the other hand, to our knowledge, the conjugate addition using enones and benzenesulfonyl chlorides as reaction partners has not been described (Scheme 1, bottom).…”

Recent advances in palladium-catalysed asymmetric 1,4–additions of arylboronic acids to conjugated enones and chromones

“…Chiral complexes of Rh [17][18][19][20][21][22][23][24] and Pd usually catalyse the reaction, however, palladium holds a special place in this area. There are several review articles partially covering this topic [25][26][27][28][29][30][31]. However, a comprehensive review is missing.…”