RESUMEN
Cycloadditions are an important class of reactions in materials science for the construction of polycyclic aromatic and polycyclic heteroaromatic compounds. Recently, cycloadditions have been expanded beyond the "classical" group of cycloadditions involving six π-electrons, and it is now possible to control cycloadditions for an extended number of π-electrons by applying organocatalysis. This novel field of cycloadditions-termed higher-order cycloadditions-allows new synthetic methodologies to construct polycyclic carbo- and heteroaromatic compounds in two or three dimensions. This concept presents higher-order cycloadditions as a method for accessing two- and three-dimensional azulenes and cyclazines, as well as three dimensional indenes, as polycyclic aromatic and polycyclic heteroaromatic compounds.
RESUMEN
The great progress that took place in the field of higher-order cycloadditions involving fulvene- and tropone-derived systems in the last few years is astonishing. By application of organocatalytic activation modes, new higher-order reactivities have been identified and described in the literature. These approaches take advantage of the high reliability of organocatalysis, at the same time expanding its potential and paving new directions for its further evolution. In this Minireview, the progress in the field of organocatalytic higher-order cycloadditions involving fulvene- and tropone-derived systems is summarized and insights into mechanistic aspects of the developed reactivities are provided. Furthermore, the discussion on the nomenclatural issues related to cycloaddition reactions has been conducted and solutions to clarify the picture proposed.
RESUMEN
A highly stereoselective 1,3-dipolar [6+4] cycloaddition towards bridged azabicyclo[4.3.1]decane scaffolds has been developed, reacting aldehydes, 2-aminomalonates and tropone under mild conditions in the presence of a chiral phosphoric acid catalyst. The scope is demonstrated for a series of aldehydes and 2-aminomalonates, and the reaction proceeds in high yields, >95:5â d.r. and up to 99 % ee. A series of transformations, as well as a mechanistic proposal, are presented.
RESUMEN
Levoglucosenone (LGO) and structurally similar exo-cyclic enones derived from cyrene (dihydrolevoglucosenone) react with tropothione following the higher-order [8 + 2]-cycloaddition pathway. Reactions were performed at room temperature in CH2Cl2 solutions in absence of any activating reagent. Whereas reaction of tropothione with LGO occurred with complete stereoselectivity, leading to a single, sterically favored exo cycloadduct, identified as polycylic thiophene derivative, reactions performed with exo-cyclic enones yielded in some instances mixtures of two isomeric exo and endo cycloadducts, derived from spiro-tetrahydrothiophene as major and minor components, respectively, of the studied reaction mixtures. Exo and endo [8 + 2] cycloadducts differ in absolute configuration at the newly created chiral centers. Structures of exo and endo cycloadducts were confirmed by single crystal X-ray diffraction analysis.