Metal-catalyzed enantioselective allylation, which involves the substitution of allylic metal intermediates with a diverse range of different nucleophiles or S(N)2'-type allylic substitution, leads to the formation of C-H, -C, -O, -N, -S, and other bonds with very high levels of asymmetric induction. The reaction may tolerate a broad range of functional groups and has been applied successfully to the synthesis of many natural products and new chiral compounds.

Metal-catalyzed enantioselective allylation in asymmetric synthesis.

Durch metallkatalysierte enantioselektive Allylierungen, die unter Substitution von Allylmetall-Zwischenstufen mit zahlreichen Nucleophilen oder als allylische SN2′-Substitution verlaufen, werden in Gegenwart ausgewahlter Kombinationen aus Metallen und chiralen Liganden C-H-, C-C-, C-O-, C-N-, C-S- und andere Bindungen mit sehr hoher asymmetrischer Induktion geknupft. Die Reaktionen sind mit einer Vielzahl funktioneller Gruppen vereinbar und wurden erfolgreich in der Synthese vieler Naturstoffe und neuer chiraler Verbindungen verwendet.

Metallkatalysierte enantioselektive Allylierungen in der asymmetrischen Synthese

The SAMP-/RAMP-hydrazone methodology in asymmetric synthesis

The well-known properties of the carbonyl group render aldehydes and ketones prominent substrates in both C-C and C-heteroatom bond forming methodologies of organic synthesis. In practical syntheses, nitrogen analogues of aldehydes and ketones such as enamines, imines, or hydrazones, acting as synthetic equivalents of the carbonyl * To whom correspondence should be addressed. E-mail: lazny@uwb.edu.pl. Chem. Rev. 2010, 110, 1386–1434 1386

N,N-dialkylhydrazones in Organic Synthesis. From Simple N,N-dimethylhydrazones to Supported Chiral Auxiliaries

[reaction: see text] Glyoxal bis(N-methyl-N-phenylhydrazone) (1) and its related compounds such as 2-pyridinecarboxaldehyde N-methyl-N-phenylhydrazone (3) were prepared and examined as ligands for the Suzuki-Miyaura cross-coupling reaction of aryl halides and arylboronic acids. We found phosphine-free catalysts, such as Pd(OAc)(2)/hydrazone ligand 1 or 3, to be efficient catalysts for a variety of substrates to produce the coupling products in good yields.

Phosphine-Free Hydrazone−Pd Complex as the Catalyst Precursor for a Suzuki−Miyaura Reaction under Mild Aerobic Conditions

Palladium-catalyzed asymmetric allylic alkylation of 1,3-diphenyl-2-propenyl acetate (4) with a dimethyl malonate−BSA−LiOAc system and its derivatives has been successfully carried out in the presence of a new chiral hydrazone ligands such as 2-(diphenylphosphino)benzaldehyde SAMP hydrazone (DPPBA-SAMP) (3a) in high yields with high enantioselectives.

Masashi Shiotsuki

Papers

Palladium-catalyzed allylic alkylation using chiral hydrazones as ligands.

Palladium‐Catalyzed Allylic Alkylation Using Chiral Hydrazones as Ligands.