The amine-catalyzed enantioselective Michael addition of aldehydes to nitro alkenes (Scheme 1) is known to be acid-catalyzed (Fig. 1). A mechanistic investigation of this reaction, catalyzed by diphenylprolinol trimethylsilyl ether is described. Of the 13 acids tested, 4-NO 2 ÀC 6 H 4 OH turned out to be the most effective additive, with which the amount of catalyst could be reduced to 1 mol-% (Tables 2 -5). Fast formation of an amino-nitro-cyclobutane 12 was discovered by in situ NMR analysis of a reaction mixture. Enamines, preformed from the prolinol ether and aldehydes (benzene/molecular sieves), and nitroolefins underwent a stoichiometric reaction to give single all-trans-isomers of cyclobutanes (Fig. 3) in a [2 þ 2] cycloaddition. This reaction was shown, in one case, to be acid-catalyzed (Fig. 4) and, in another case, to be thermally reversible (Fig. 5). Treatment of benzene solutions of the isolated aminonitro-cyclobutanes with H 2 O led to mixtures of 4-nitro aldehydes (the products 7 of overall Michael addition) and enamines 13 derived thereof (Figs. 6 -9). From the results obtained with specific examples, the following tentative, general conclusions are drawn for the mechanism of the reaction (Schemes 2 and 3): enamine and cyclobutane formation are fast, as compared to product formation; the zwitterionic primary product 5 of C,C-bond formation is in equilibrium with the product of its collapse (the cyclobutane) and with its precursors (enamine and nitro alkene); when protonated at its nitronate anion moiety the zwitterion gives rise to an iminium ion 6, which is hydrolyzed to the desired nitro aldehyde 7 or deprotonated to an enamine 13. While the enantioselectivity of the reaction is generally very high (> 97% ee), the diastereoselectivity depends upon the conditions, under which the reaction is carried out (Fig. 10 and Tables 1 -5). Various acid-catalyzed steps have been identified. The cyclobutanes 12 may be considered an off-cycle reservoir of catalyst, and the zwitterions 5 the key players of the process (bottom part of Scheme 2 and Scheme 3).

The aza-Diels Alder reaction has become one of the most widely used synthetic tools for the preparation of N-containing 6-membered heterocycles. Numerous important developments have been reported to render this reaction catalytic and enantioselective. This tutorial review highlights strategies and recent advances to achieve high efficiency and selectivity through the use of organocatalysts and transition metal complexes, allowing also the extension of this transformation substrate scope.

There is much concern about the toxicological effects of synthetic hair dyes. As an alternative approach, renewable waste blackcurrant ( Ribes nigrum L.) fruit skins from the fruit pressing industry were extracted using acidified water with a solid-phase purification stage. Anthocyanin colorants were isolated in good yields (2-3% w/ w) and characterized by HPLC. Sorption of anthocyanins onto hair followed a Freundlich isotherm; anthocyanin-anthocyanin aggregation interactions enabled high buildup on the substrate. Sorption energy of cyanidin-3- O-glucoside (monosaccharide) > cyanidin-3- O-rutinoside (disaccharide), but sorption properties of different anthocyanin glucosides were very similar. Intense blue-colored dyeing on hair could be achieved with λ at 580 nm, typical of the anionic quinonoid base; it is suggested that hair provides an environment that enables the stabilization of the anionic quinonoid base on adsorption through association with cations in the hair and copigmentation effects. Dyeings were stable to multiple washes.