Chiral primary β‐amino alcohols, constuting adjacently positioned Brønsted base and Brønsted acid sites, are emerging as very valuable bifunctional organocatalysts in a wide array of asymmetric organic transformations. Primary β‐amino alcohols represent inexpensive alternatives to other primary amino organocatalysts such as chiral diamines and cinchona‐alkaloid‐derived primary amines, being easy to synthesize and air‐stable and offering the potential for introduction of different functional groups and also for alteration of steric sites. Here we reveal the catalytic use of simple primary β‐amino alcohols and their derivatives as organocatalysts in Diels–Alder cycloaddition, aldol condensation, Michael addition, 1,3‐dipolar cycloaddition, the Morita–Baylis–Hillman reaction, cascade cyclization, allylation of isatins, Friedel–Crafts alkylation and epoxidation of olefins.

Enantioselective aldol reactions of various isatins with ketones using newly designed amino amide organocatalysts were found to provide chiral 3‐substituted 3‐hydroxy‐2‐oxindoles in good to excellent yields and with excellent stereoselectivities (up to 99 %, up to 98 % ee, syn/anti = 99:1); one catalyst, 3i, proved particularly successful. One of the resulting oxindoles, 3‐hydroxy‐3‐(2‐oxocyclohexyl)‐2‐indolinone may serve as a synthetic intermediate for pharmaceutically important compounds and, in its own right, shows interesting anticonvulsant activities.

Enantioselective crossed aldol reactions of isatin derivatives and acetaldehyde have been developed with a series of simple diamino alcohol catalysts to afford 3‐substituted 3‐hydroxyindolin‐2‐ones in high chemical yields (up to 95 %) and optical purities (up to 92 % ee). The synthetic potential of the present protocol has been demonstrated by concise, enantioselective, protecting‐group‐free, and transition metal‐free total syntheses of antitumor and antiviral agents with the tryptanthrin architecture, that is, phaitanthrin B and cephalanthrin A, along with the biologically active indolidine alkaloids chimonamidine and donaxaridine as well as the formal synthesis of CPC‐1. The highly enantioselective outcome of this catalytic crossed aldol reaction was evaluated by calculating the Gibbs free energies of the possible transition states.

A simple and efficient method for the a-thiocyanation of ketones has been developed; anhydrous iron(III) chloride is used under mild conditions to produce a-oxo thiocyanates in good to high yields and with high selectivity. The use of inexpensive and readily available iron(III) chloride makes this procedure simple, convenient, and practical.

A short and efficient approach for the total synthesis of two novel cytotoxic hydroquinones, lanneaquinol (1) and (R)‐2′‐hydroxylanneaquinol (2) isolated from the organic extract of the plant Lannea welwitschii, has been developed. Enantioselective organocatalytic McMillan hydroxylation has been successfully utilized for the creation of the stereogenic center bearing the OH group of (R)‐2′‐hydroxylanneaquinol (2). The hydroquinone core was constructed through the alkylation of cyclohexane‐1,4‐dione with a corresponding aldehyde. Both hydroquinone natural products can be synthesized by a mere change in the synthetic strategy.