Since the turn of the millennium, catalytic reactions promoted by primary or secondary amines have emerged as a highly useful method for organic chemistry. Very recently, the potential of such synthetic strategies has been vastly expanded by incorporating the principle of aromaticity breaking. Novel reaction pathways can now be accessed through the intermediacy of polyenamine intermediates derived from (hetero)aromatic systems. The proper design of carbonyl starting materials, combined with the high stereochemical efficiency provided by well-established aminocatalysts, has enabled the synthesis of products with (hetero)aromatic frameworks in highly enantio- and diastereomerically enriched form. In this Minireview, we provide an overview of recent advances in this field of research and familiarize the reader with new synthetic opportunities offered by these interesting methodologies.
A new approach for the stereoselective remote alkylation of furan derivatives is reported. The reaction of 5-alkylfurfurals with nitroolefins as electrophilic counterparts occurs at their exocyclic ε-position and proceeds through the intermediacy of a nonclassical catalytic trienamine intermediate. The aminocatalyst bearing a H-bonding unit is used to control the stereochemical reaction outcome confirming the usefulness of such catalytic systems for the remote functionalizations of carbonyl compounds. Target products with two adjacent stereogenic centers are obtained in excellent yields and with good to moderate stereoselectivities.
1,3-Dipolar cycloaddition constitutes powerful means for the synthesis of five-membered heterocycles. Recently, the potential of this field of chemistry has been expanded by the employment of organocatalytic activation strategies. One...
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