Recent developments in the synthesis and utilization of chiral sulfoxides.

Catalytic Enantioselective Formation of C−C Bonds by Addition to Imines and Hydrazones: A Ten-Year Update

Despite the impressive progress achieved in asymmetric catalysis during the last decade, an increasing number of new catalysts, ligands, and applications are reported every year to satisfy the need to embrace a wider range of reactions and to improve the efficiency of existing processes. Because of their availability, unique stereochemical aspects, and wide variety of coordination modes and possibilities for the fine-tuning of the steric and electronic properties, ferrocene-based ligands constitute one of the most versatile ligand architectures in the current scenario of asymmetric catalysis. Over the last few years ferrocene catalysts have been successfully applied in an amazing variety of enantioselective processes. This Review documents these recent advances, with special emphasis on the most innovative asymmetric processes and the development of novel, efficient types of ferrocene ligands.

Recent applications of chiral ferrocene ligands in asymmetric catalysis.

Chiral sulfur ligands for asymmetric catalysis.

Recent developments in catalytic asymmetric inverse-electron-demand Diels-Alder reaction.

An efficient chiral Lewis acid-catalyzed inverse-electron-demand Diels−Alder reaction of 1-azadienes is described. This procedure is based on the combination of NiII-DBFOX complex as catalyst and the use of a metal-coordinating (8-quinolyl)sulfonyl moiety at the iminic nitrogen of the N-sulfonyl 1-aza-1,3-diene, providing highly functionalized piperidine derivatives in good yields with excellent endo-selectivity, and enantioselectivities typically in the range of 77−92% ee.

Catalytic asymmetric inverse-electron-demand Diels-Alder reaction of N-sulfonyl-1-aza-1,3-dienes.

Palladium Complexes of Chiral Planar 1-Phosphino-2-sulfenylferrocenes as Efficient Catalysts in Enantioselective Diels-Alder Reactions

The highly diastereoselective DIBALH and DIBALH/ZnBr2 reduction of enantiomerically pure (5S,(S)S)-3-ethoxy-5-(p-tolylsulfinyl)cyclopentenone (9) is used as a key step to the synthesis of oxazolidinone 2, a precursor of glycosidase inhibitor mannostatin. Compound 9 was obtained from 3-ethoxycyclopentenone by direct sulfinylation with (S)-N-benzyl-N-(p-tolylsulfinyl)propionamide.

and Ramón Gómez Arrayás

Papers

Catalytic asymmetric inverse-electron-demand Diels-Alder reaction of N-sulfonyl-1-aza-1,3-dienes.

Palladium Complexes of Chiral Planar 1-Phosphino-2-sulfenylferrocenes as Efficient Catalysts in Enantioselective Diels-Alder Reactions

Sulfoxide-Mediated Asymmetric Synthesis of Glycosidase Inhibitor Precursors