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A new organocatalytic cascade reaction for obtaining spiropyrazolones with four chiral centers is developed.

TFA catalyzes the alkylation of oxazolones, oxindoles, benzofuranones, and pyrazolones by carbocations generated in situ from alcohols (II) or (XIII), to give the corresponding derivatives bearing a quaternary carbon center.

Bifunctional amino-thiourea-catalyzed reaction of anthrones (I) and (IV) with β-nitrostyrene derivatives (II) exclusively affords the Michael adducts (III) and (V), respectively.

The title compounds are obtained through a Michael—Michael-aldol reaction in good yields and with high diastereo- and enantioselectivity.

The title reaction affords spirooxindole derivatives in good yields and with high diastereo- and enantioselectivity.

A new, practical and enantioselective entry to direct precursors of quaternary α-alkyl-α-amino acids is developed.

The first highly diastereo- and enantioselective organocatalytic synthesis of 2,2-disubstituted-2H-oxazol-5-ones is described. The addition of oxazolones to maleimides is promoted by bifunctional thiourea catalysts, which afford the corresponding 2,2-disubstituted-2H-oxazol-5-ones with total regio- and stereocontrol.

In spite of the tremendous growth experienced by the field of asymmetric organocatalysis in the last decade, it is important to realize that we are still far away from having explored all of the possible pathways in organocatalysis ‘territory'; the application of the organocatalysis concept can still provide new catalysts and reactions for a variety of asymmetric organic transformations. To exemplify this assertion, we summarize the research performed in our laboratory over the past two years which has led to the development of new enantioselective approaches to organometallic compounds, to the desymmetrization of prochiral ketones, to functionalized cyclopropanes and piperidines, to fluorinated compounds, and to quaternary ?-amino acids, among others.

The development of new asymmetric methodologies that afford different structures in an enantioselective fashion is one of the most exciting goals for chemists nowadays. In this subject, lately, the use of sulfones has become a fast growing field. From the works of Tan and Shibata until the last works of Palomo, sulfones have demonstrated their versatility and power in organocatalytic asymmetric reactions. Moreover, the easy removal of sulfones with Mg or Hg/Na makes this group a perfect choice to afford easily naked alkyls. Remarkably, bissulfones can be used as nucleophiles or electrophiles, being vinyl sulfones excellent electrophiles, while bismethylensulfones derivatives such as fluoro are excellent nucleophiles. This double possibility has been studied by several research groups, leading to new methodologies that allow obtaining formally simple alkylation in an enantioselective fashion, by using organocatalysis. The aim of this tutorial review is to summarize the last trends in the use of sulfones in organocatalytic processes, giving a complete scenario of these new reagents.

A new, easy, and highly enantioselective method for the synthesis of quaternary α-alkyl-α-amino acids based on organocatalysis is described.

For the first time, the addition of anthrones to maleimides catalyzed by bifunctional thiourea catalysts is reported. The thiourea moiety is able to activate the maleimide and the tertiary amine deprotonates the anthrone, furnishing the final Diels–Alder or Michael adducts in excellent yields and enantioselectivities.

Since the serendipitous discovery of ferrocene by Pauson and Kealy in 1951, it has become one of the most important structures in Organic Chemistry. Lately, kinetic resolution has emerged as a useful tool for the synthesis of planar chiral ferrocenes. This review aims to cover and discuss the development of this topic.

A highly enantioselective organocatalytic oxindole addition to α,β-unsaturated aldehydes is reported. The reaction is catalyzed by simple and commercially available chiral secondary amines, affording the corresponding adducts with good yields and with moderate diastereoselectivities.

A convenient and novel domino reaction for the synthesis of highly functionalized cyclopropanes is reported. The addition of 2-bromoketo esters to a variety of ?,?-unsaturated aldehydes catalyzed by secondary amines leads to chiral cyclopropanes with three stereogenic carbon atoms, including one quaternary stereocenter, in a highly stereocontrolled fashion.

The first examples of enantioselective addition of anthrones to α,β-unsaturated aldehydes are disclosed. The reaction was performed at −40 °C achieving high yields and enantioselectivities.