Recent advances in the organocatalytic applications of cyclopropene- and cyclopropenium-based small molecules.

The development of novel small molecule-based catalysts for organic transformations has increased noticeably in the last two decades. A very recent addition to this particular research area is cyclopropene- and cyclopropenium-based catalysts. At one point in time, particularly in the mid-20th century, much attention was focused on the structural aspects and physical properties of cyclopropene-based compounds. However, a paradigm shift was observed in the late 20th century, and the focus shifted to the synthetic utility of these compounds. In fact, a wide range of cyclopropene derivatives have been found serving as valuable synthons for the construction of carbocycles, heterocycles and other useful organic compounds. In the last few years, the catalytic applications of cyclopropene/cyclopropenium-based compounds have been uncovered and many synthetic protocols have been developed using cyclopropene-based compounds as organocatalysts. Therefore, the main objective of this review is to highlight recent developments in the catalytic applications of cyclopropene-based small molecules in different areas of organocatalysis such as phase-transfer catalysis (PTC), Brønsted base catalysis, hydrogen-bond donor catalysis, nucleophilic carbene catalysis, and electrophotocatalysis developed within the past two decades.

Understanding cyclic(alkyl)(amino)carbene-copper complex catalysed N-H and O-H bond addition to electron deficient olefins.

The hydroamination of electron-deficient olefins was carried out using the (CAAC)Cu-Cl (CAAC = cyclic (alkyl)(amino)carbene) catalyst with an excellent yield at room temperature and under an open atmosphere. Furthermore, the catalyst shows excellent efficiency in the hydroaryloxylation and hydroalkoxylation of alkenes under mild conditions. The efficiency of the catalyst was tested for a wide range of substrates with different electronic and steric functionalities. Detailed computational studies have been carried out to understand the mechanism of these Cu(I) catalyzed reactions, which revealed that the reaction proceeds via either a four-membered or a six-membered cyclic transition state containing the copper ion.

Palladium complexes with an annellated mesoionic carbene (MIC) ligand: catalytic sequential Sonogashira coupling/cyclization reaction for one-pot synthesis of benzofuran, indole, isocoumarin and isoquinolone derivatives.

Two Pd(ii) complexes (1 and 2) featuring a fused π-conjugated imidazo[1,2-a][1,8]naphthyridine-based mesoionic carbene ligand have been synthesized and structurally characterized. Both complexes effectively catalyze the one-pot synthesis of benzofuran starting from phenylacetylene and 2-iodophenol under mild conditions. Complex 1 is found to be an excellent catalyst for the straightforward access to a library of benzofuran, indole, isocoumarin and isoquinolone derivatives by the reaction of terminal alkynes with 2-iodo derivates of phenol, N-methyl aniline, benzoic acid and N-methyl benzamide, respectively. The general utility of the catalytic method is demonstrated using a variety of diversely substituted terminal alkynes and the corresponding desired products are obtained in good to excellent yields. On the basis of control experiments, a two-cycle mechanism is proposed which involves the Sonogashira coupling of 2-iodo derivatives with alkynes and the subsequent cyclization of the corresponding 2-alkynyl compounds.